Zeolite formed product, zeolite laminate intermediate, zeolite laminate composite and method for their preparation

ABSTRACT

A porous zeolite shaped body of a zeolite is characterized in that the porous zeolite shaped body is made of a completely crystallized zeolite or a zeolite still under crystallization and composed of tetrapropylammonium ion (TPA) and silica sol in a mixing ratio (TPA/SiO 2 ) of 0.015 to 0.08 by mole: a zeolite shaped body has an average particle diameter of 1.0 μm or larger, a bending strength of 1.5 MPa or higher, and a difference in pressure between a feed side and a permeation side of 1.0 atmospheric pressure or lower at 10 ml/cm 2 .min of helium gas permeation flux when a thickness of the porous zeolite shaped body is adjusted to be 1.8 mm: and a zeolite shaped body has 70% or more of the area of the parts (the sound parts) where respective particles are clearly observed by grain boundary fracture among particles composing the shaped body in the entire area of the fractured surface in microstructure observation of the fractured surface of the shaped body itself.

TECHNICAL FIELD

[0001] The present invention relates to a zeolite shaped body, a zeolitelayered intermediate body, a zeolite-layered composite, and productionmethods for them. More particularly, the present invention relates to azeolite shaped body capable of forming a zeolite membrane thereonwithout causing cracking, and satisfactorily reducing pressure loss andmaintaining and improving mechanical strength when it is used as a gasseparation membrane of a molecular sieve membrane and a pervaporationmembrane and the like; a zeolite layered intermediate body comprisingthe zeolite shaped body and a zeolite membrane containing a template andlayered thereon; a zeolite layered composite formed by calcining thezeolite layered intermediate body, and their efficient productionmethods.

BACKGROUND ART

[0002] Recently, a zeolite shaped body composed of particles of azeolite has been employed widely for catalysts, catalyst carriers,adsorbents and the like. Also, a zeolite layered composite comprising aporous ceramic, a metal, or the like and a zeolite membrane layeredthereon has been employed for a molecular sieve membrane (a gasseparation membrane, a pervaporation membrane). Along with theproceeding of such situation, there proposed are zeolite-layeredcomposites using a variety of porous substrates and their productionmethods.

[0003] For example, proposed are methods using glass, mullite, acordierite type ceramic, alumina, silica, and the like as a substratefor a zeolite membrane and methods using a metal or another substratecoated with an inorganic substance (Japanese Patent Laid-Open No.59-213615).

[0004] Also, proposed (JP-A-60-28826) are composites each comprising aporous supporting body of a metal, an inorganic or polymer substance anda thin membrane of a cage type zeolite integrated in one surface. Amongthem, those having high affinity for a gel substance are proposed asespecially preferable ones for the supporting body to be used andpractically, it is proposed to use No. 7930 product produced by CorningGlass Works, generally called Vycorl glass, as especially preferableone.

[0005] Further, a method proposed (JP-A-1-148771) relates to a methodfor crystallization of zeolite on the surface of a monolithic ceramicsupporting body as a substrate which may have an oxide compositioncontaining 4 to 45% by weight of silica, 8 to 45% by weight of alumina,and 7 to 20% by weight of magnesia; and practically proposed is asintered monolithic supporting body of cordierite, glass, or a glassceramic.

[0006] Further, another method proposed (Japanese Patent Laid-Open No.6-32610) relates to a method for production of an A-type or faujasitetype zeolite membrane using a substrate of a substance mainly containingsilicon oxide. The method aims to solve the problem of inferior adhesionstrength of a zeolite membrane to a substrate, wherein a zeolitemembrane is used as a substrate itself and the substrate surface is madeto be a zeolite membrane owing to its constitution, thereby thesynthesis and the adhesion can simultaneously be carried out to simplifythe processes. To be practically, a substrate made of borosilicateglass, quartz glass, silica-alumina, mullite or the like is proposed.

[0007] Further, there is another proposal (JP-A-9-173799) which relatesa production method of a carrier zeolite membrane, and a membrane as thecarrier, comprises an inorganic, organic, or mixed substance selectedfrom the group consisting of a ceramic substance basically containingalumina, zirconia, or titanium oxide; a metal; carbon; silica; azeolite; a clay; and a polymer.

[0008] Further, proposed is a zeolite porous body which is a porousceramic substrate subjected to conversion treatment to a zeolite and hasa large number of inner holes with prescribed sizes and a compressivefracture strength of 5 MPa or higher (JP-A-11-292651).

[0009] As described above, a variety of zeolite layered composites eachcomprising a substrate and a zeolite membrane layered or formed thereonhave been proposed, however these composites have the followingproblems.

[0010] That is, as shown in FIG. 16, the thermal expansion coefficientof a zeolite shows rather complicated behavior; at a temperature toaround 200° C., it is extremely low but it becomes a negativecoefficient value at a temperature further higher than that. Hence, if azeolite membrane is to be used at a temperature exceeding 200° C., thethermal expansion coefficient difference becomes extremely high betweena substrate, for example, an alumina-based substrate and the membrane,resulting in cracking of the zeolite membrane owing to the thermalstress.

[0011] Further, depending on the types of zeolite membranes, at the timeof synthesis, a casing agent or a crystallization promoting agent isrequired to be added. In the case of a zeolite membrane containing atemplate, the template is removed by calcining at about 500° C. and asshown in the thermal expansion curve of a MFI type zeolite in FIG. 17,the thermal expansion behavior (the thermal expansion curve before thecalcining in FIG. 17) of a zeolite membrane containing a templatesignificantly differs from the thermal expansion behavior (the thermalexpansion curve after the calcining in FIG. 17) of a zeolite membranecontaining no template, so that the thermal expansion difference becomesextremely wide between a substrate of such as an alumina substrate andthe zeolite membrane and cracking takes place in the zeolite membraneowing to the thermal stress at the time of the calcining.

[0012] To such problems, said proposal examples cannot be sufficientcountermeasures to deal with the problems.

[0013] Further, the following are proposed as examples of those havingdouble layer structure of a substrate and a zeolite membrane: asymmetricmembranes (JP-A-7-505333) each comprising a macroporous layer formedpractically only from a molecular sieve crystal with a prescribedthickness and an upper layer for molecular separation having aprescribed thickness and a prescribed effective diameter of fine poresand formed practically only from the molecular sieve crystal of the sametype as that of the material of the macroporous layer; a structure(JP-K-11-511685) composed of three layers, a carrier, an intermediatelayer, and an upper layer and in which the intermediate layer and theupper layer contain prescribed crystalline molecular sieves; and azeolite composite membrane (International Laid-open No. WO 00/23378)produced by forming a zeolite membrane containing a template on azeolite shaped body containing a template and then calcining to form themembrane and simultaneously remove the template. These membranes andstructure are respectively excellent in the properties; the capabilityof precisely adjusting the size of the fine pores and the capability ofeffectively preventing occurrence of cracking.

[0014] However, regarding the zeolite shaped body obtained as thezeolite composite membrane (International Laid-open No. WO 00/23378)formed simultaneously with removal of the template from said substrate,since the raw materials (a dried gel) are obtained by stirring andkneading preparation solutions of silica sol and tetrapropylammoniumhydroxide (TPAOH), the obtained dried gel is easy to contain particleswith different particle diameter and heterogenously dried state, so thatdense and sparse parts and degranulated parts are easily formed in thezeolite particle portions in the microstructure after thecrystallization treatment and therefore it is not necessarilysatisfactory one.

[0015] Further, regarding a method including processes of previouslydispersing a template such as tetrapropylammonium (TPA) in a dried geland then converting it to a zeolite by treatment with steam, since ithas conventionally been thought necessary to stir a mixture solution ofa gel and a template until they are dried as a dried gel productionprocess, the following processes have generally been employed; heatingmixture solution of the gel and the template to about 80° C. toevaporate water and successively continuously stirring (kneading) thesolution until the mixture is sufficiently dried [N. Jappar, Q. Xia, andT. Tatsumi, J. Catal. 180, 132-141 (1998); R. Bandyopadhyay et al.,Micropor. Mater. 32(1999) 81-91; Masahiko Matsukata, P. R. H. PrasadRao, Korekazu Ueyama, Proceedings of the 11th Zeolite Research Meeting,Japan Association of Zeolite, in Matsuyama, 1995, A22; P. R. H. PrasadRao, Proceedings of the 12th Zeolite Research Meeting, Japan Associationof Zeolite, at Sophia University, 1996, A18.; P. R. Hari Prasad Rao & M.Matukata, Chem. Commun. (1996), p1441-1442, P. R. Hari Prasad Rao, K.Ueyama, M. Matsukata, Appl. Catal. A: General 166 (1998) 97-103; and thelike].

[0016] However, such a method comprising the dried gel productionprocess comprises complicated production process and is thus notsuitable for mass production and further, the obtained dried gel is, assame as the case of said International Laid-open No. WO 00/23378, easyto be heterogenous in the size of the particle diameter and nothomogeneous in the dried state and for that, in the micro-structureafter the crystallization treatment, dense and sparse parts anddegranulated parts are easily formed among the zeolite particle portionsand the method is not necessarily satisfactory.

[0017] Further, in the case where the membranes or the structure(zeolite layered composites) are used as gas separation membranes ofmolecular sieve membranes and pervaporation membranes, it is required toimprove the use efficiency by decreasing the pressure loss at the timeof passing a gas or a liquid through the membranes and the substrate. Ifthe dense parts of particles of the substrate, which are causes ofincrease of the pressure loss, are reduced or the particle size of thesubstrate is enlarged in order to reduce the pressure loss, themechanical strength as a substrate for supporting a zeolite membrane isdecreased (the reduction in the pressure loss in the substrate and theimprovement of the mechanical strength are in an antinomic relation), sothat it is extremely difficult to obtain those capable of satisfyingboth of the reduction in the pressure loss and the improvement of themechanical strength and any membrane or structure capable of satisfyingsuch properties has not been obtained so far.

[0018] The present invention is developed in consideration of saidproblems and aims to provide a zeolite shaped body by forming a zeolitemembrane thereon without causing cracking, and capable of satisfactorilyreducing pressure loss and improving mechanical strength when it is usedas a gas separation membrane of a molecular sieve membrane, and apervaporation membrane and the like; a zeolite layered intermediate bodycomprising the zeolite shaped body and a zeolite membrane containing atemplate and layered thereon; a zeolite layered composite formed bycalcining the zeolite layered intermediate body, and their efficientproduction methods.

DISCLOSURE OF THE INVENTION

[0019] In order to achieve said purposes, according to the presentinvention, provided are a zeolite shaped body, a zeolite layeredintermediate body, a zeolite layered composite, and production methodsfor them.

[0020] [1] A porous zeolite shaped body of a zeolite, characterized inthat a porous zeolite shaped body is made of a completely crystallizedzeolite composed of tetrapropylammonium ion (TPA) and silica sol in amole ratio (TPA/SiO₂) of 0.015 to 0.08.

[0021] [2] A porous zeolite shaped body of a zeolite, characterized inthat a porous zeolite shaped body is made of a zeolite still under thecrystallization and composed of tetrapropylammonium ion (TPA) and silicasol in a mole ratio (TPA/SiO₂) of 0.02 to 0.12.

[0022] [3] A zeolite intermediate body, characterized in that thezeolite shaped body as described in [1] or [2] contains further atemplate, and a template-containing zeolite membrane having acomposition the same as or similar to that of the shaped body is formedthereon.

[0023] [4] A zeolite layered composite comprising said zeolite shapedbody and said zeolite membrane layered thereon, characterized in thatthe composite is produced by removing said template from said zeoliteshaped body and said template-containing zeolite membrane by calciningthe zeolite layered intermediate body as described in [3].

[0024] [5] A method for producing a zeolite layered compositecharacterized by layering a template-containing zeolite membrane havinga composition the same as or similar to that of a zeolite shaped body ofa completely crystallized zeolite composed of tetrapropylammonium ion(TPA) and silica sol in a mole ratio (TPA/SiO₂) of 0.015 to 0.08 andcontaining a template therein on said zeolite shaped body, andsimultaneously removing the template from said zeolite membrane and saidzeolite shaped body by calcining the resulting layered product to obtainthe zeolite layered composite comprising said zeolite shaped body andsaid zeolite membrane layered thereon.

[0025] [6] A method for producing a zeolite layered compositecharacterized by layering a template-containing zeolite membrane havinga composition the same as or similar to that of a zeolite shaped body ofa zeolite still under crystallization and composed oftetrapropylammonium ion (TPA) and silica sol in a mixing ratio(TPA/SiO₂) of 0.02 to 0.12 by mole and containing a template therein onsaid zeolite shaped body, and simultaneously removing the template fromsaid zeolite membrane and said zeolite shaped body by calcining theresulting layered product to obtain the zeolite layered compositecomprising said zeolite shaped body and said zeolite membrane layeredthereon.

[0026] [7] A porous zeolite shaped body of a zeolite, characterized inthat the porous zeolite shaped body has an average particle diameter of1.0 μm or larger, a bending strength of 1.5 MPa or higher, and adifference in pressure between a feed side and a permeation side of 1.0atmospheric pressure or lower at 10 ml/cm² min of helium gas permeationflux when a thickness of the porous zeolite shaped body is adjusted tobe 1.8 mm.

[0027] [8] A zeolite layered intermediate body, characterized in thatthe zeolite shaped body as described in [7] contains further a template,and a template-containing zeolite membrane having a composition the sameas or similar to that of the shaped body is layered thereon.

[0028] [9] A zeolite layered composite comprising said zeolite shapedbody and said zeolite membrane layered thereon, characterized in thatthe zeolite layered composite is formed by removing said template fromsaid zeolite shaped body and said template-containing zeolite membraneby calcining the zeolite layered intermediate body as described in [8].

[0029] [10] A method for producing a zeolite shaped body characterizedby adding a tetrapropylammonium hydroxide (TPAOH) solution andtetrapropylammonium bromide (TPABr) to silica sol in such a manner thatmixing ratios [TPAOH/(TPAOH+TPABr) and TPABr/(TPAOH+TPABr)] oftetrapropylammonium hydroxide (TPAOH) and tetrapropylammonium bromide(TPABr) to a total amount of tetrapropylammonium ion (TPA) become 0 to99% by mole and 1 to 100% by mole, respectively to prepare a solution,drying the prepared solution by kneading the solution, shaping theobtained dried gel, and subjecting the shaped body to crystallizationtreatment.

[0030] [11] A method for producing a zeolite shaped body, characterizedby adding a tetrapropylammonium hydroxide (TPAOH) solution to silica solto prepare a solution, spraying the prepared solution to dry, shapingthe obtained dried gel, and subjecting the shaped body tocrystallization treatment.

[0031] [12] A method for producing a zeolite layered intermediate body,characterized by adding a tetrapropylammonium hydroxide (TPAOH) solutionand tetrapropylammonium bromide (TPABr) to silica sol in such a mannerthat mixing ratios [TPAOH/(TPAOH+TPABr) and TPABr/(TPAOH+TPABr)] oftetrapropylammonium hydroxide (TPAOH) and tetrapropylammonium bromide(TPABr) to a total amount of tetrapropylammonium ion (TPA) become 0 to99% by mole and 1 to 100% by mole, respectively to prepare a solution,drying the prepared solution by kneading the solution, shaping theobtained dried gel, subjecting the shaped product to crystallizationtreatment to obtain a zeolite shaped body, immersing said zeolite shapedbody in a solution having the same or similar composition as or to saidprepared solution, and forming a template-containing zeolite membrane onsaid zeolite shaped body by hydrothermally synthesizing it thereon toproduce a layered body comprising said zeolite shaped body and saidtemplate-containing zeolite membrane.

[0032] [13] A method for producing a zeolite layered intermediate body,characterized by adding a tetrapropylammonium hydroxide (TPAOH) solutionto silica sol, spraying thus prepared solution to dry, shaping theobtained dried gel, subjecting the shaped product to crystallizationtreatment to obtain a zeolite shaped body, immersing said zeolite shapedbody in a solution with the same or similar composition as or to that ofsaid solution, and forming a template-containing zeolite membrane on thezeolite shaped body by hydrothermally synthesizing it thereon to producea layered body comprising said zeolite shaped body and saidtemplate-containing zeolite membrane.

[0033] [14] A method for producing a zeolite layered composite,characterized by adding a tetrapropylammonium hydroxide (TPAOH) solutionand tetrapropylammonium bromide (TPABr) to silica sol in such a mannerthat the mole ratio of mixing ratios [TPAOH/(TPAOH+TPABr) andTPABr/(TPAOH+TPABr)] of tetrapropylammonium hydroxide (TPAOH) andtetrapropylammonium bromide (TPABr) to a total amount oftetrapropylammonium ion (TPA) become 0 to 99% and 1 to 100%,respectively to prepare a solution, drying the prepared solution bykneading the solution, shaping the obtained dried gel, subjecting theshaped body to crystallization treatment to obtain a zeolite shapedbody, immersing said zeolite shaped body in a solution with the same orsimilar composition as or to that of said solution, forming atemplate-containing zeolite membrane on the zeolite shaped body byhydrothermally synthesizing it thereon to produce a layered bodycomprising said zeolite shaped body and said template-containing zeolitemembrane, and then calcining the layered body to simultaneously removingthe template.

[0034] [15] A method for producing a zeolite layered composite,characterized by adding a tetrapropylammonium hydroxide (TPAOH) solutionto silica sol to prepare a solution, spraying thus prepared solution todry, shaping the obtained dried gel, subjecting the shaped product tocrystallization treatment to obtain a zeolite shaped body, immersingsaid zeolite shaped body in a solution having the same or similarcomposition as or to that of said prepared solution, forming atemplate-containing zeolite membrane on the zeolite shaped body byhydrothermally synthesizing it thereon to produce a layered bodycomprising said zeolite shaped body and said template-containing zeolitemembrane, and then calcining the layered body to simultaneously removingthe template.

[0035] [16] A porous zeolite shaped body of a zeolite, characterized inthat area of parts (sound parts) where respective particles are clearlyobserved by grain boundary fracture among particles composing thezeolite shaped body in microstructure observation of the fracturedsurface of the shaped body occupies 70% or more in the entire area ofthe fractured surface.

[0036] [17] A zeolite layered intermediate body, characterized in thatthe zeolite shaped body as described in [16] contains a template, and atemplate-containing zeolite membrane having a composition the same as orsimilar to that of the shaped body is formed on the shaped body.

[0037] [18] A zeolite layered composite comprising a zeolite shaped bodyand a zeolite membrane formed thereon, characterized in that the zeolitelayered composite is produced by removing said template from saidzeolite shaped body and said template-containing zeolite membrane bycalcining the zeolite layered intermediate body as described in [17].

[0038] [19] A method for producing a zeolite shaped body characterizedby adding a tetrapropylammonium hydroxide (TPAOH) solution to silica solin such a manner that a mixing ratio (TPA/SiO₂) of tetrapropylammoniumion (TPA) to the silica sol becomes 0.015 to 0.08 by mole to prepare asolution, drying the prepared solution by kneading the solution, wetpulverizing the obtained dried gel, drying the obtained slurry byspraying the slurry, shaping the obtained dried granular substance, andsubjecting thus shaped body to crystallization treatment.

[0039] [20] A method for producing a zeolite shaped body, characterizedby adding a tetrapropylammonium hydroxide (TPAOH) solution to silica solin such a manner that a mixing ratio (TPA/SiO₂) of tetrapropylammoniumion (TPA) to the silica sol becomes 0.015 to 0.08 by mole to prepare asolution, spraying thus prepared solution to dry, shaping the obtaineddried gel, and subjecting thus shaped body to crystallization treatment.

[0040] [21] A method for producing a zeolite layered intermediate body,characterized by adding a tetrapropylammonium hydroxide (TPAOH) solutionto silica sol in such a manner that a mixing ratio (TPA/SiO₂) oftetrapropylammonium ion (TPA) to the silica sol becomes 0.015 to 0.08 bymole to prepare a solution, drying the prepared solution by kneading thesolution, wet pulverizing the obtained dried gel, spraying the obtainedslurry to dry, shaping the obtained dried granular substance, subjectingthus shaped product to crystallization treatment to obtain a zeoliteshaped body, immersing said zeolite shaped body in a solution with thesame or similar composition as or to said prepared solution, and forminga template-containing zeolite membrane on the zeolite shaped body byhydrothermally synthesizing it thereon to produce a layered bodycomprising the zeolite shaped body and the template-containing zeolitemembrane.

[0041] [22] A method for producing a zeolite layered intermediate bodycharacterized by adding a tetrapropylaimonium hydroxide (TPAOH) solutionto silica sol in such a manner that a mixing ratio (TPA/SiO₂) oftetrapropylammonium ion (TPA) to the silica sol becomes 0.015 to 0.08 bymole to prepare a solution, spraying thus prepared solution to dry,shaping the obtained dried gel, subjecting thus shaped product tocrystallization treatment to obtain a zeolite shaped body, immersingsaid zeolite shaped body in a solution having the same or similarcomposition as or to that of said prepared solution, and forming atemplate-containing zeolite membrane on the zeolite shaped body byhydrothermally synthesizing it thereon to produce a layered bodycomprising the zeolite shaped body and the template-containing zeolitemembrane.

[0042] [23] A method for producing a zeolite layered composite,characterized by adding a tetrapropylammonium hydroxide (TPAOH) solutionto silica sol in such manner that a mixing ratio (TPA/SiO₂) oftetrapropylammonium ion (TPA) to the silica sol becomes 0.015 to 0.08 bymole to prepare a solution, drying the prepared solution by kneading thesolution, wet pulverizing the obtained dried gel, drying the obtainedslurry by spraying the slurry, shaping the obtained dried granularsubstance, subjecting thus shaped product to crystallization treatmentto obtain a zeolite shaped body, immersing said zeolite shaped body in asolution having the same or similar composition as or to that of saidprepared solution, and forming a template-containing zeolite membrane onthe zeolite shaped body by hydrothermally synthesizing it thereon toproduce a layered body comprising the zeolite shaped body and thetemplate-containing zeolite membrane, and then simultaneously removingthe template by calcining the layered body.

[0043] [24] A method for producing a zeolite layered composite,characterized by adding a tetrapropylammonium hydroxide (TPAOH) solutionto silica sol in such manner that a mixing ratio (TPA/SiO₂) oftetrapropylammonium ion (TPA) to the silica sol becomes 0.015 to 0.08 bymole to prepare a solution, spraying thus prepared solution to dry,shaping the obtained dried gel, subjecting thus shaped product tocrystallization treatment to obtain a zeolite shaped body, immersingsaid zeolite shaped body in a solution with the same or similarcomposition as or to that of said solution, forming atemplate-containing zeolite membrane on the zeolite shaped body byhydrothermally synthesizing it thereon to produce a layered bodycomprising the zeolite shaped body and the template-containing zeolitemembrane, and then simultaneously removing the template by calcining thelayered body.

BRIEF DESCRIPTION OF THE DRAWINGS

[0044]FIG. 1 is a SEM photograph showing the microstructure of thefractured surface of a zeolite layered intermediate body obtained inexample 12 of the first invention. FIG. 2 is a graph showing the x-raydiffraction pattern to show that is of a MFI type zeolite membrane.

[0045]FIG. 3 shows a graph showing the relation between the mixing ratioof tetrapropylammonium bromide (TPABr) to the total amount oftetrapropylammonium ion (TPA), that is, the mixing ratio[TPABr/(TPAOH+TPABr)] to (TPAOH+TPABr), and the average particlediameter in the zeolite shaped bodies obtained in examples 14 to 19 ofthe second invention and comparative example 16.

[0046]FIG. 4 to FIG. 8 are SEM photographs showing the microstructure ofthe fractured surface of each zeolite shaped body obtained in examples14 to 18 of the second invention.

[0047]FIG. 9 shows a graph showing the relation between the mixing ratio(TPABr/TPA) of tetrapropylammonium bromide (TPABr) to the total amountof tetrapropylammonium ion (TPA) and the bending strength of eachzeolite shaped body obtained in examples 14 to 19 of the secondinvention and comparative example 16.

[0048]FIG. 10 shows a graph showing the relation between the averageparticle diameter and the four-point bending strength in each zeoliteshaped body obtained in examples 14 to 19 of the second invention andcomparative example 16.

[0049]FIG. 11 shows a graph showing the relation between the averageparticle diameter and the pressure loss in each zeolite shaped bodyobtained in examples 14 to 20 of the second invention and comparativeexample 16.

[0050]FIG. 12 to FIG. 14 show SEM photographs showing the microstructureof the fractured surface of each zeolite shaped body obtained inexamples 19 to 20 of the second invention and comparative example 16.

[0051]FIG. 15 is a schematic figure illustrating the crack measurementmethod by a pervaporation method.

[0052]FIG. 16 is a graph showing the thermal expansion curve of a MFItype zeolite.

[0053]FIG. 17 is a graph showing the thermal expansion curves of a MFItype zeolite (before calcining and after calcining) and that of alumina.

[0054]FIG. 18 shows a SEM photograph showing the method for measuringthe average particle diameter.

[0055]FIG. 19 is a replicated figure of the SEM photograph showing themethod for measuring the average particle diameter.

[0056]FIG. 20 is a schematic figure illustrating the method formeasuring the average particle diameter.

[0057]FIG. 21 is a schematic figure illustrating the method formeasuring the pressure loss. FIG. 22 is a SEM photograph showing themicrostructure of the fractured surface of zeolite layered intermediatebody obtained in example 21 of the second invention.

[0058]FIG. 23 is a graph showing the particle degree distribution of theslurry obtained in the example 23 of the third invention.

[0059]FIG. 24 is a SEM photograph showing the microstructure of theouter surface of the dried gel obtained in example 23 of the thirdinvention.

[0060]FIG. 25 and FIG. 26 are SEM photographs showing the microstructureof the fractured surface of the zeolite shaped body obtained in example23 of the third invention.

[0061]FIG. 27 is a SEM photograph showing the microstructure of theouter surface of the dried gel obtained in example 24 of the thirdinvention.

[0062]FIG. 28 and FIG. 29 are SEM photographs showing the microstructureof the fractured surface of the zeolite shaped body obtained in example24 of the third invention.

[0063]FIG. 30 is a SEM photograph showing the microstructure of theouter surface of the dried gel obtained in comparative example 17 of thethird invention.

[0064]FIG. 31 and FIG. 32 are SEM photographs showing the microstructureof the fractured surface of the zeolite shaped body obtained incomparative example 17 of the third invention.

[0065]FIG. 33 is a SEM photograph illustrating the method for measuringthe homogeneity in the fractured surface of a zeolite shaped bodyobtained.

[0066]FIG. 34 is a replicated figure of a SEM photographs illustratingthe method for measuring the homogeneity in the fractured surface of azeolite shaped body obtained.

[0067]FIG. 35 is a SEM photograph showing the microstructure of thefractured surface of the zeolite layered intermediate body obtained inexample 25 of the third invention.

BEST MODE FOR CARRYING OUT THE INVENTION

[0068] Since a zeolite shaped body of the invention is to be effectivelyused as a substrate in form of a zeolite layered composite by layeringor forming a zeolite membrane thereon for a gas separation membrane of amolecular sieve membrane and a pervaporation membrane, it is required toprevent cracking in the zeolite to be layered or formed thereon. Forthat, a zeolite shaped body of the invention is preferable to be aporous zeolite composed of particles of a zeolite with the compositionsame as or similar to that of the zeolite membrane to be layered thereonin the case where it is used for obtaining a zeolite layered compositeby layering the zeolite membrane thereon.

[0069] Especially, in the case where a zeolite layered composite isformed using a template, in consideration of that the thermal expansionbehavior of a template-containing zeolite membrane is extremelydifferent from that of a zeolite membrane containing no template asshown in FIG. 17, only using a substrate (for example, quartz glass andthe like) with the thermal expansion coefficient approximate to that ofthe zeolite membrane is insufficient to solve the thermal expansiondifference at the time of calcining at about 500° C. for removal of thetemplate and consequently cracking takes place in the zeolite membrane,and therefore, a zeolite shaped body of the invention is preferably aporous zeolite with the composition same as or similar to that of thezeolite membrane in the entire respect with the composition includingthe template.

[0070] A zeolite shaped body of the invention is a porous zeolite shapedbody of a zeolite, characterized by being made of a completelycrystallized zeolite and composed of tetrapropylammonium ion (TPA) andsilica sol in the mixing ratio (TPA/SiO₂) of 0.015 to 0.08 by mole or aporous zeolite shaped body of a zeolite characterized by being made of azeolite still under crystallization and composed of tetrapropylammoniumion (TPA) and silica sol in the mixing ratio (TPA/SiO₂) of 0.02 to 0.12by mole (hereinafter, this invention is sometimes referred as to “thefirst invention”).

[0071] Consequently, since a zeolite shaped body of the first inventionis provided with the strength increased to 1.5 MPa or higher, a zeolitemembrane can be formed thereon even under hydrothermal environmentswithout being damaged and in addition to that, even after the zeolitemembrane is formed, the resulting shaped body can retain the function ofthe membrane without damaging the zeolite membrane.

[0072] Incidentally, regarding the crystalline phase of a zeolite, theterm, “a completely crystallized zeolite”, means those having all of thesharp peaks, which show a zeolite, clearly observed in x-ray diffractionin a range of 20 to 30° (CuKα) and having no halo and the term, “azeolite still under the crystallization”, means those having peaks of azeolite even though a few and in this case, the zeolite has compoundeddiffraction patterns in which halo showing amorphous, which will bedescribed later, and sharp peaks showing a zeolite are overlaid in termsof x-ray diffraction. Incidentally, those other than the aboveexemplified ones having only broad halo but no clear peak observed means“an amorphous zeolite”.

[0073] Further, a zeolite layered intermediate body of the firstinvention is characterized in that said zeolite shaped body contains atemplate and a template-containing zeolite membrane with a compositionthe same as or similar to that the zeolite membrane is layered on theshaped body.

[0074] Further, a zeolite layered composite of the first invention ischaracterized by comprising a zeolite membrane formed on a zeoliteshaped body and being produced by removing the template from the zeoliteshaped body and the template-containing zeolite membrane by calciningsaid zeolite layered intermediate body.

[0075] Although a zeolite to be used for the first invention is notparticularly restricted, effectively usable in the first invention are,for example, MFI, AFI, DDR and the like (reference to Park S. H. et al.Stud. Surf. Sci. Catal. 1997, 105, 1989-1994), whose thermal expansionshows unique nonlinear behavior, since it is generally difficult toprevent occurrence of cracking in a zeolite membrane in the case where azeolite layered composite is produced from a zeolite membrane usingthese zeolites and a zeolite shaped body as a substrate.

[0076] Further, in the case where a template is required at the time ofzeolite membrane formation, usable as the template are ahydroxide[tetrapropylammonium hydroxide (TPAOH)] orbromide[tetrapropylammonium bromide (TPABr)]of tetrapropylammonium to beadded to a MFI type zeolite membrane, a hydroxide or bromide oftetraethylammonium (TEA) to be added to a BEA type zeolite, and azeolite membrane containing such a template and a zeolite membranecontaining no template are significantly different from each other, asshown in FIG. 17, in the thermal expansion behavior.

[0077] Consequently, as a zeolite shaped body of the first invention,preferable to be used are, in the case where MFI, AFI, DDR, or the likeand containing a template is used and a zeolite membrane is layered orformed thereon to be employed for a zeolite layered composite, zeoliteshaving the same or similar compositions even including addition of atemplate same as that of the zeolite membrane, and preferable to be usedare, in the case where MFI, AFI, DDR, or the like and containing notemplate is used and a zeolite membrane is layered or formed thereon tobe employed for a zeolite layered composite, zeolites having the same orsimilar compositions even including addition of no template.

[0078] Further, the production method of a zeolite layered composite ofthe first invention comprises a process of layering atemplate-containing zeolite membrane with a composition the same as orsimilar to that of a template-containing zeolite shaped body of acompletely crystallized zeolite composed of tetrapropylammonium ion(TPA) and silica sol in the mixing ratio (TPA/SiO₂) of 0.015 to 0.08 bymole or that of a template-containing zeolite shaped body of a zeolitestill under crystallization and composed of tetrapropylammonium ion(TPA) and silica sol in the mixture ratio (TPA/SiO₂) of 0.02 to 0.12 bymole on either one of the described zeolite shaped bodies andsimultaneously removing the template from said zeolite membrane and saidzeolite shaped body by calcining the resulting layered product.

[0079] As a method for layering a zeolite membrane on a zeolite shapedbody, a conventionally known method can be employed and, for example, ahydrothermal synthesis method, a vapor phase transport method may beemployed.

[0080] Further, as a method for producing the zeolite shaped body, thefollowing methods are known and any one may be employed:

[0081] (1) a method of hardening a zeolite powder with a binder;

[0082] (2) a method of converting a binder into a zeolite by chemicaltreatment after a zeolite powder is hardened with the binder; and

[0083] (3) a method of shaping a zeolite precursor and converting it toa zeolite by heat treatment.

[0084] Regarding said binder addition method (1), examples are a methodof adding a sol such as silica sol to a zeolite (See JP-A-2-4445), amethod of adding attapulgite type clay and carboxymethyl cellulose to azeolite (See JP-A-10-81511), and the like.

[0085] Regarding the binder-less method (2), examples are a method ofmixing kaolin with a zeolite, firing the mixture, and then convertingkaolin to a zeolite by alkaline hydrothermal treatment (SeeJP-A-10-101326), a method of mixing a zeolite with metakaolin and thenconverting metakaolin to a zeolite by alkaline treatment (SeeJP-A-52-103391), and the like.

[0086] Further, regarding the zeolite solid-phase synthesis method (3),examples are a method for obtaining a zeolite of such as MFI and thelike by mixing a template to kanemite to obtain an amorphous silicatepowder and heat treatment it after shaping it (See JP-B-2725720), amethod for obtaining a zeolite by mixing a template to TEOS, hydrolyzingthe mixture, shaping the mixture, and then heat treatment it (referenceSimizu, S., Kiyozumi Y. & Mizukami F. Chem. Lett. 1996, 403-404) and thelike.

[0087] A zeolite shaped body of the invention is a porous zeolite shapedbody of a zeolite, characterized by having an average particle diameterof 1.0 μm or larger, a bending strength of 1.5 MPa or higher, and adifference in pressure between a feed side and a permeation side of 1.0atmospheric pressure or lower at 10 ml/cm² min of helium gas permeationflux when a thickness of the porous zeolite shaped body is adjusted tobe 1.8 mm (hereinafter, the invention is also referred as to “the secondinvention”).

[0088] As a template if necessary to be used at the time of forming azeolite to be employed for the second invention and a zeolite membrane,usable are those same as the first invention.

[0089] A zeolite shaped body of the second invention has an averageparticle diameter of 1.0 μm or larger, preferably 2.5 μm or larger,; abending strength of 1.5 MPa or higher, preferably 6.0 MPa or higher, anda difference in pressure between a feed side and a permeation side of1.0 atmospheric pressure or lower, preferably 0.6 atmospheric pressureor lower, at 10 ml/cm² min of helium gas permeation feed when itsthickness is adjusted to be 1.8 mm.

[0090] By satisfying these conditions, a zeolite shaped body of thesecond invention enables to form a zeolite membrane thereon withoutcausing cracking, and capable of satisfactorily reducing pressure lossand improving mechanical strength when it is used as a gas separationmembrane of a molecular sieve membrane and a pervaporation membrane andthe like.

[0091] Incidentally, the average particle diameter is calculated bymeasuring the maximum length of each particle and averaging themeasurement result using an image analyzer. That is, the fracturedsurface of a zeolite shaped body of the second invention (partsextracted at random) is observed by a scanning electron microscope (SEM)and photographed to obtain SEM photographs (FIG. 18). Based on the SEMphotograph, a replicated figure divided into white and black parts isproduced (FIG. 19). In this case, the white parts show the particles andthe black parts show the voids and unclear parts among particles, andparticles whose entire portion are seen are selected and if the entireportion is not seen, particles of which at least the maximum particlediameter can be observed are selected. Further, the particles which areoverlapped and whose entire portion are unclear are omitted for themeasurement. For the image analysis, as an apparatus, animage analyzer(trade name: Image Analyzer V10, manufactured by Toyobo Co., Ltd.) isused to input the replicated image into a personal computer and themeasurement region, the scale and the binary treatment are set (thetreatment for identifying the white parts of the replicated figure aszeolite particles and the black parts as non-measured parts of such asvoids among particles) to measure the maximum length of the respectiveparticles according to the standards shown in FIGS. 20(a) to (c) andcalculate the average particle diameter.

[0092] The bending strength is measured according to JIS R 1601.

[0093] Further, the pressure loss is measured by a method shown in FIG.21.

[0094] That is, a zeolite shaped body 11 (18 mm of diameter, 1.8 mm ofthickness) of the second invention and a quartz glass tube 12 are joinedwith epoxy resin and disposed in a container 13 made of a metal (astainless steel). At room temperature, helium gas is used as a feed gas14 and the pressure is increased to at highest 8 kgf/cm², and thepressure of the feed gas 14 is measured by a pressure gauge 16, thepressure of the permeating gas 15 is measured by a pressure gauge 17,and the permeation flux is measured by a flow meter 18. The differencein pressure between the feed side and the permeation side at 10 ml/cm²min of helium gas permeation flux is defined as the pressure loss.

[0095] Incidentally, since the pressure loss of a porous material isincreased in proportion to the thickness of a measurement specimen (thepressure loss increases two times high, if the thickness increases twotimes thick), the thickness of a measurement specimen is required to bealways constant or correction by calculation is required inconsideration of the thickness. In the second invention, the thicknessof a specimen is made even to be 1.8 mm and with such a shape, thepressure difference between the feed side and the permeation side ismeasured and the value is defined as the pressure loss.

[0096] The zeolite shaped body production method of the second inventioncomprises processes of adding a tetrapropylammonium hydroxide (TPAOH)solution and tetrapropylammonium bromide (TPABr) to silica sol in such amanner that the mole ratio of mixing ratios [TPAOH/(TPAOH+TPABr) andTPABr/(TPAOH+TPABr)] of tetrapropylammonium hydroxide (TPAOH) andtetrapropylammonium bromide (TPABr) to the total amount oftetrapropylammonium ion (TPA) become 0 to 99% and 1 to 100%,respectively, drying the produced solution by kneading, shaping theobtained dried gel, and subjecting the shaped body to crystallizationtreatment.

[0097] In this case, the mixing ratio (TPA/SiO₂ mole ratio) of thetetrapropylammonium ion (TPA) and silica sol may be adjustable in anyrange within a range of 0.015 to 0.08 by mole since the average particlediameter of the zeolite shaped body is not changed and the bendingstrength is 1.5 MPa or higher, which is required for a substrate to beused for production of a zeolite layered composite, (the strength highenough to avoid the damage of a zeolite membrane in hydrothermalsynthesis environments and the damage even after membrane formation). Inthe embodiments of the second invention, TPA/SiO₂ is adjusted to be 0.04by mole ratio at which the bending strength becomes the maximum.

[0098] If the mole ratio of TPA/SiO₂ and the respective ratios of TPAOHand TPABr to the total amount of TPA of a produced solution are kept inprescribed values, respectively, an alkaline source such as sodiumhydroxide, potassium hydroxide, and the like may be added to adjust pH,if necessary.

[0099] Then, in order to dry the produced solution, the producedsolution is added to a Teflon beaker and stirred by a magnetic stirrerand then, while being heated in a thermostat at a prescribedtemperature, the solution is continuously manually stirred with a Teflonrod and kneaded to evaporate water and obtain a dried gel. The stirringand kneading in this case may be carried out using a heating kneader orthe like.

[0100] Then, the dried gel is shaped by properly forming the gel in aprescribed shape by a uniaxial pressing with a die (the total pressure1,000 kgf) and then carrying out cold isostatic pressing to obtain adried gel shaped body. At this time, the pressure of the cold isostaticpressing is preferable to be adjusted within a range of 700 to 7,000kgf/cm² so as to make the resulting dried gel shaped body to have adesired density.

[0101] Then, the dried gel shaped body obtained in the manner asdescribed above is put on a Teflon plate so as to keep the shaped bodyfrom water in a Teflon inner cylinder-attached pressure vessel made of astainless steel and storing distilled water in the same weight as thatof the shaped body and reaction is caused under spontaneous steampressure for 10 hours in an oven at 180° C. and crystallization iscarried out to obtain a zeolite shaped body. The amount of the distilledwater at this time is the minimum level of the amount with which thesteam pressure reaches the saturated pressure for the volume of thepressure vessel used and if the amount is that level or higher, there isno particular restriction in terms of the relation of a shaped body anddistilled water. Further, regarding the reaction temperature and time,since crystallization proceeds at 130° C. or higher for 2 hours orlonger, the temperature and the time are not particularly restricted ifthey are the above mentioned levels or more, respectively.

[0102] The zeolite shaped body production method of the second inventionmay comprise processes of adding a tetrapropylammonium hydroxide (TPAOH)solution to silica sol in such a manner that the mole ratio of mixingratio (TPA/SiO₂) of tetrapropylammonium ion (TPA) to the silica solbecomes a prescribed value, spraying thus prepared solution to dry,shaping the obtained dried gel, and subjecting thus obtained gel tocrystallization treatment to obtain a product.

[0103] As the method for spraying thus prepared solution to dry, usableis, for example, a spraying and drying apparatus for a solution and aslurry such as a spray drier, a fluid bed granulation dryer and thelike. To dry the produced solution in the second invention, a spraydrier is used. The produced solution is transported to a spraying nozzletip by a liquid sending pump, and the solution is sprayed from a nozzletip by pressurized air, dried in a drying chamber where dry air iscirculated, and recovered. At this time, the air circulated in thedrying chamber is previously heated to 180° C. in the periphery of thespraying port of the produced solution and the pressurized air, howeverthe temperature may be changed depending on the volume of the dryingchamber and it is therefore not particularly restricted.

[0104] In this case, the mixing ratio (TPA/SiO₂ mole ratio) of thetetrapropylammonium ion (TPA) and silica sol may be adjustable in anyrange within a range of 0.015 to 0.08 by mole since the average particlediameter of the zeolite shaped body is not changed and the bendingstrength is 1.5 MPa or higher, which is required for a substrate to beused for production of a zeolite layered composite. In the examples ofthe second invention, the mole ratio of TPA/SiO₂ is adjusted to be 0.04at which the bending strength becomes the maximum.

[0105] If the mole ratio of TPA/SiO₂ is kept in prescribed values, analkaline source such as sodium hydroxide, potassium hydroxide, and thelike may be added to adjust pH based, if necessary.

[0106] Then, the produced solution is sprayed and dried by said sprayingmethod to obtain a dried gel.

[0107] Then, the dried gel is shaped by properly forming the gel in aprescribed shape by a uniaxial pressing with a die (the total pressure1,000 kgf) and then carrying out cold isostatic pressing to obtain adried gel shaped body. At this time, the pressure of the cold isostaticpressing is preferable to be adjusted within a range of 700 to 7,000kgf/cm² so as to make the resulting dried gel shaped body to have adesired density.

[0108] Then, the dried gel shaped body obtained in the manner asdescribed above is put on a Teflon plate so as to keep the shaped bodyfrom water in a Teflon inner cylinder-attached pressure vessel made of astainless steel and storing distilled water in the same weight as thatof the shaped body and reaction is caused under spontaneous steampressure for 10 hours in an oven at 180° C. and crystallization iscarried out to obtain a zeolite shaped body. The amount of the distilledwater at this time is the minimum level of the amount with which thesteam pressure reaches the saturated pressure for the volume of thepressure vessel used and if the amount is that level or higher, there isno particular restriction in terms of the relation of a shaped body anddistilled water. Further, regarding the reaction temperature and time,since crystallization proceeds at 130° C. or higher for 2 hours orlonger, the temperature and the time are not particularly restricted ifthey are the above mentioned levels or more, respectively.

[0109] The method for drying by spraying in such a manner can carry outdrying more and prevent the microstructure after the crystallizationtreatment more efficiently from being coarsened and degranulated thansaid method for drying by kneading.

[0110] A zeolite layered intermediate body of the second invention ischaracterized by comprising said zeolite shaped body containing atemplate and a template-containing zeolite membrane with the compositionsame as or similar to that of the shaped body layered on the shapedbody.

[0111] As a formation method of the template-containing zeolitemembrane, the same method as that in the first invention may beemployed.

[0112] Further, a zeolite layered composite of the second invention ischaracterized by comprising a zeolite shaped body a zeolite membranelayered on the shaped body and being produced by removing the templatefrom the zeolite shaped body and the zeolite-containing zeolite membraneby calcining said zeolite layered intermediate body.

[0113] In this case, since a zeolite layered composite is to be employedfor a gas separation membrane of a molecular sieve membrane and apervaparation membrane, a template-containing zeolite membrane or azeolite membrane, from which the template is removed, to be layered on azeolite shaped body is required to have sufficient thickness so as toprevent exposure of the zeolite shaped body and to be a dense membrane.Further, in the case where those containing a template are used as azeolite shaped body, a template-containing zeolite membrane to belayered thereon is required to be made of a zeolite with the compositionsame as or similar to that of the zeolite shaped body, including thatthe membrane contains the same template (that is same in the case of thefirst invention and also in the case of the third invention which willbe described later.).

[0114] A zeolite layered intermediate body production method of thesecond invention is characterized by comprising the processes of addinga tetrapropylammonium hydroxide (TPAOH) solution and tetrapropylammoniumbromide (TPABr) to silica sol in such a manner that the mole ratio ofmixing ratio (TPA/SiO₂) of tetrapropylammonium ion (TPA) of them and thesilica sol becomes a prescribed value, and the respective mixing ratios[TPAOH/(TPAOH+TPABr) and TPABr/(TPAOH+TPABr)] of tetrapropylammoniumhydroxide (TPAOH) and tetrapropylammonium bromide (TPABr) to the totalamount of tetrapropylammonium ion (TPA) become 0 to 99% and 1 to 100%,respectively, drying the produced solution by kneading the solution,shaping the obtained dried gel, subjecting the shaped product tocrystallization treatment to obtain a zeolite shaped body, immersing theobtained zeolite shaped body in a solution with the same or similarcomposition as or to that of the solution, and forming atemplate-containing zeolite membrane on the zeolite shaped body byhydrothermally synthesizing it thereon to produce a layered bodycomprising the zeolite shaped body and the template-containing zeolitemembrane. More exemplified explanation will be given in the descriptionof a zeolite layered composite production method of the secondinvention.

[0115] Further, the method may be a one, characterized by comprising theprocesses of adding a tetrapropylammonium hydroxide (TPAOH) solution tosilica sol in such a manner that the mixing ratio (TPA/SiO₂) oftetrapropylammonium ion (TPA) to the silica sol becomes a prescribedvalue, spraying thus prepared solution to dry, shaping the dried gel,subjecting the shaped product to crystallization treatment to obtain azeolite shaped body, immersing the obtained zeolite shaped body in asolution with the same or similar composition as or to that of theprepared solution, and forming a template-containing zeolite membrane onthe zeolite shaped body by hydrothermally synthesizing it thereon toproduce a layered body comprising the zeolite shaped body and thetemplate-containing zeolite membrane. More exemplified explanation willbe given in the description of a zeolite layered composite productionmethod of the second invention.

[0116] A zeolite layered composite production method of the secondinvention is characterized by comprising the processes of adding atetrapropylammonium hydroxide (TPAOH) solution and tetrapropylammoniumbromide (TPABr) to silica sol in such a manner that the mixing ratio(TPA/SiO₂) of tetrapropylammonium ion (TPA) of them to the silica solbecomes a prescribed value and the respective mixing ratios[TPAOH/(TPAOH+TPABr) and TPABr/(TPAOH+TPABr)] of tetrapropylammoniumhydroxide (TPAOH) and tetrapropylammonium bromide (TPABr) to the totalamount of tetrapropylammonium ion (TPA) become 0 to 99% by mole and 1 to100% by mole, respectively, drying thus prepared solution by kneadingthe solution, shaping the obtained dried gel, subjecting the shapedproduct to crystallization treatment to obtain a zeolite shaped body,immersing the obtained zeolite shaped body in a solution with the sameor similar composition as or to that of the prepared solution, forming atemplate-containing zeolite membrane on the zeolite shaped body byhydrothermally synthesizing it thereon to produce a layered bodycomprising the zeolite shaped body and the template-containing zeolitemembrane, and then simultaneously removing the template from the layeredbody by calcining.

[0117] In this case, the mixing ratio (TPA/SiO₂ mole ratio) of thetetrapropylammonium ion (TPA) and silica sol may be adjustable in anyrange within a range of 0.015 to 0.08 by mole since the average particlediameter of the zeolite shaped body is not changed and the bendingstrength is 1.5 MPa or higher, which is required for a substrate to beused for production of a zeolite layered composite. In the embodimentsof the second invention, the mole ratio of TPA/SiO₂ is adjusted to be0.04 at which the bending strength becomes the maximum.

[0118] If the mole ratio of TPA/SiO₂ and the respective ratios of TPAOHand TPABr to the total amount of TPA of a produced solution are kept inprescribed values, respectively, an alkaline source such as sodiumhydroxide, potassium hydroxide, and the like may be added to adjust pH,if necessary.

[0119] Then, in order to dry the produced solution, the producedsolution is added in a Teflon beaker and stirred by a Teflon rod andthen, while being heated in a thermostat at a prescribed temperature,the solution is continuously manually stirred and kneaded to evaporatewater and obtain a dried gel. The stirring and kneading in this case maybe carried out using a heating kneader or the like.

[0120] Then, the dried gel is shaped by properly forming the gel in aprescribed shape by a uniaxial pressing with a die (the total pressure1,000 kgf) and then carrying out cold isostatic pressing to obtain adried gel shaped body. At this time, the pressure of the cold isostaticpressing is preferable to be adjusted within a range of 700 to 7,000kgf/cm² so as to make the resulting dried gel shaped body to have adesired density.

[0121] Then, the dried gel shaped body obtained in the manner asdescribed above is put on a Teflon plate so as to keep the shaped bodyfrom water in a Teflon inner cylinder-attached pressure vessel made of astainless steel and storing distilled water in the same weight as thatof the shaped body and reaction is caused under spontaneous steampressure for 10 hours in an oven at 180° C. and crystallization iscarried out to obtain a zeolite shaped body. The amount of the distilledwater at this time is the minimum level of the amount with which thesteam pressure reaches the saturated pressure for the volume of thepressure vessel used, and if the amount is that level or higher, thereis no particular restriction in terms of the relation of a shaped bodyand distilled water. Further, regarding the reaction temperature andtime, since crystallization proceeds at 130° C. or higher for 2 hours orlonger, the temperature and the time are not particularly restricted ifthey are the above mentioned levels or more, respectively.

[0122] A template-containing zeolite is layered on the zeolite shapedbody obtained in the manner as described above by adding a TPAOHsolution, TPABr, and distilled water to silica sol in such a amount thatthe mole ratio of SiO₂/TPAOH/TPABr/water becomes a prescribed value toprepare a mixed solution, charging thus obtained solution to a pressurevessel, immersing the zeolite shaped body in the produced solution,causing reaction for 1 hour or longer in an oven at 100° C. or higher toform a sufficiently thick and dense layer of a template-containingzeolite membrane on the zeolite shaped body and to obtain a zeolitelayered intermediate body, calcining the zeolite layered intermediatebody to obtain a zeolite layered composite. In the examples of thesecond invention, reaction is carried out for 18 hours in an oven at180° C. to form a dense layer of a zeolite membrane with the thicknessof 20 μm or thicker on the zeolite shaped body.

[0123] Incidentally, if the mole ratio of SiO₂/tetrapropylammonium ion(TPA)/water is kept in prescribed value, an alkaline source such assodium hydroxide, potassium hydroxide, and the like may be added toadjust pH, if necessary.

[0124] Further, as the method for zeolite membrane formation, the samemethod as that of the first invention may be employed.

[0125] The zeolite layered composite production method of the secondinvention may comprise processes of adding a tetrapropylammoniumhydroxide (TPAOH) solution to silica sol in such a manner that the moleratio of mixing ratio (TPA/SiO₂) of tetrapropylammonium ion (TPA) to thesilica sol become a prescribed value, spraying thus prepared solution todry, shaping the obtained dried gel, and subjecting thus shaped productto crystallization treatment to obtain a zeolite shaped body, immersingthe obtained zeolite shaped body in a solution with the same or similarcomposition as or to that of the solution, forming a template-containingzeolite membrane on the zeolite shaped body by hydrothermallysynthesizing it thereon to produce a layered body comprising the zeoliteshaped body and the template-containing zeolite membrane, andsimultaneously removing the template by calcining the obtained layeredbody.

[0126] Incidentally, in the zeolite shaped body production, the mixingratio (TPA/SiO₂ mole ratio) of the tetrapropylammonium ion (TPA) andsilica sol may be adjustable in any range within a range of 0.015 to0.08 by mole since the average particle diameter of the zeolite shapedbody is not changed and the bending strength is 1.5 MPa or higher, whichis required for a substrate to be used for production of a zeolitelayered composite. In the examples of the second invention, TPA/SiO₂mole ratio is adjusted to be 0.04 at which the bending strength becomesthe maximum.

[0127] Then, for drying the produced solution, a spray dryer is used.The produced solution is sprayed by pressurized air and dried in adrying chamber where dry air is circulated. At this time, the aircirculated in the drying chamber is previously heated to 180° C. in theperiphery of the spraying port, however the temperature may be changeddepending on the volume of the drying chamber and it is therefore notparticularly restricted.

[0128] Then, the dried gel is shaped by properly forming the gel in aprescribed shape by a uniaxial pressing with a die (the total pressure1,000 kgf) and then carrying out cold isostatic pressing to obtain adried gel shaped body. At this time, the pressure of the cold isostaticpressing is preferable to be adjusted within a range of 700 to 7,000kgf/cm² so as to make the resulting dried gel shaped body to have adesired density.

[0129] Then, the dried gel shaped body obtained in the manner asdescribed above is put on a Teflon plate so as to keep the shaped bodyfrom water in a Teflon inner cylinder-attached pressure vessel made of astainless steel and storing distilled water in the same weight as thatof the shaped body and reaction is caused under spontaneous steampressure for 10 hours in an oven at 180° C. and crystallization iscarried out to obtain a zeolite shaped body. The amount of the distilledwater at this time is the minimum level of the amount with which thesteam pressure reaches the saturated pressure for the volume of thepressure vessel used and if the amount is that level or higher, there isno particular restriction in terms of the relation of a shaped body anddistilled water. Further, regarding the reaction temperature and time,since crystallization proceeds at 130° C. or higher for 2 hours orlonger, the temperature and the time are not particularly restricted ifthey are the above mentioned levels or more, respectively.

[0130] A template-containing zeolite is layered on thus obtained zeoliteshaped body by adding a TPAOH solution, TPABr, and distilled water tosilica sol in such a manner that the mole ratio ofSiO₂/TPAOH/TPABr/water becomes a prescribed value, adjusting the mixedsolution, loading the obtained solution to a pressure vessel, immersingthe zeolite shaped body in the produced solution, causing reaction for 1hour or longer in an oven at 100° C. or higher to form a sufficientlythick and dense layer of a template-containing zeolite membrane on thezeolite shaped body and to obtain a zeolite layered intermediate body,calcining the zeolite layered intermediate body to obtain a zeolitelayered composite and then calcining the zeolite layered intermediatebody to obtain a zeolite layered composite. In the examples of thesecond invention, reaction is carried out for 18 hours in an oven at180° C. to form a dense layer of a zeolite membrane with the thicknessof 20 μm or thicker on the zeolite shaped body.

[0131] Incidentally, if the mole ratio of SiO₂/tetrapropylammonium ion(TPA)/water is kept in prescribed value, an alkaline source such assodium hydroxide, potassium hydroxide, and the like may be added toadjust pH, if necessary.

[0132] Further, as the method for zeolite membrane formation, the samemethod as that of the first invention may be employed.

[0133] A zeolite shaped body of the invention is a porous zeolite shapedbody composed of particles of a zeolite and is characterized in that thearea of the parts (the entirely sound parts) where respective particlesare clearly observed by grain boundary fracture among particlescomposing said zeolite shaped body in microstructure observation of thefractured surface of the shaped body occupies 70% or more in the entirearea of the fractured surface (hereinafter, the invention is sometimesreferred as to the third invention.).

[0134] If a template is required at the time of zeolite or zeolitemembrane formation to be employed for the third invention, as thetemplate, those same as used for the first and the second inventions maybe employed.

[0135] A zeolite shaped body of the third invention is characterized inthat the area of the parts (the entirely sound parts) where respectiveparticles are clearly observed by grain boundary fracture amongparticles composing said zeolite shaped body in microstructureobservation of the fractured surface of the shaped body occupies 70% ormore in the entire area of the fractured surface.

[0136] As described above, since a zeolite shaped body of the thirdinvention has the area of the entirely sound parts in microstructure ofthe fractured surface of 70% or more in the entire area of the fracturedsurface, degranulation and formation of coarse parts scarcely take placeto give homogeneous microstructure in the fractured surface, and capableof satisfactorily reducing pressure loss and improving mechanicalstrength.

[0137] Incidentally, in the third invention, the homogeneity in themicrostructure of said fractured surface is calculated by observing themicrostructure of the fractured surface of a zeolite shaped body by ascanning electron microscope (SEM) and calculating the ratio of the areaof the entirely sound parts to the entire area of the fractured surfaceusing an image analyzer.

[0138] That is, the fractured surface of a zeolite shaped body of thethird invention is observed by a scanning electron microscope (SEM) andin order to make the entire microstructure observable, SEM photographsare taken while the zeolite particles with the diameter of about 1 μmbeing magnified in 1,500 or less magnification and those with thediameter of about 8 μm being magnified in 500 or less magnification(FIG. 33). Using the SEM photographs as bases, replicated figures eachdivided into white and black parts are produced (FIG. 34).

[0139] In this case, the white parts show the sound parts (the partswhere the respective particles are clearly observed by grain boundaryfraction) and the black parts show the dense parts (the parts where therespective particles are not clearly observed by grain boundaryfraction). For the image analysis, as an apparatus, an image analyzer(trade name: Image Analyzer V10, manufactured by Toyobo Co., Ltd.) isused to input the replicated images into a personal computer and themeasurement region, the scale and the binary treatment are set (thetreatment for identifying the white parts of the replicated figures aszeolite particles and the black parts as non-measured parts, that is,dense parts) to measure the ratio of the area of the sound parts to theentire surface of the fractured surface.

[0140] The bending strength is measured according to JIS R 1601.

[0141] Further, the pressure loss is measured in the same manner as thecase of the second invention.

[0142] A zeolite shaped body of the third invention has the area of thesound parts in microstructure of the fractured surface preferably of 70%or more in the entire area of the fractured surface and more preferably90% or more, a bending strength preferably of 1.5 MPa or higher and morepreferably 6.0 MPa or higher, and a difference in pressure between thefeed side and the permeation side (pressure loss) preferably of 1.0atmospheric pressure or lower and more preferably 0.6 atmosphericpressure lower at 10 ml/cm².min of helium gas permeation flux when thethickness is adjusted to be 1.8 mm.

[0143] A zeolite shaped body production method of the third invention ischaracterized by comprising the processs of adding a tetrapropylammoniumhydroxide (TPAOH) solution to silica sol in such a manner that the moleratio of mixing ratio (TPA/SiO₂) of tetrapropylammonium ion (TPA) tosaid silica sol becomes 0.015 to 0.08, preferably 0.02 to 0.06, dryingthe prepared solution by kneading the solution, wet pulverizing theobtained dried gel, spraying thus obtained slurry to drying, shapingthus obtained dried granular substance, and subjecting thus shaped bodyto crystallization treatment.

[0144] In this case, as a method for drying a slurry by spraying, usableis, for example, a spraying and drying apparatus for a solution and aslurry such as a spray drier, a fluid bed granulation dryer and thelike. To dry the produced slurry in the third invention, a spray drieris used. The produced slurry is transported to a spraying nozzle tip bya liquid sending pump, and the slurry is sprayed from a nozzle tip,dried in a drying chamber where dry air is circulated, and recovered. Atthis time, the air circulated in the drying chamber is previously heatedto 180° C. in the periphery of the spraying port of the slurry and thepressurized air, however the temperature may be changed depending on thevolume of the drying chamber and it is therefore not particularlyrestricted.

[0145] Further, the spray drying of a slurry by a spray drier is knownas a granulation method for a ceramic fine powder suitable for pressingand since granulation can be performed by instantaneous heat drying, thedrying is not affected by the raw material composition. Consequently,even in the case of the raw material containing silica sol andtetrapropylammonium ion (TPA), if the composition has the prescribedmixing ratio (TPA/SiO₂ mole ratio), a zeolite shaped body can beobtained by spraying, drying and subjecting to crystallization treatmentindependently of the TPA raw material.

[0146] More practically, at first, silica sol and a tetrapropylammoniumhydroxide (TPAOH) solution are mixed. At this time, if the mixing ratio(TPA/SiO₂ mole ratio) of tetrapropylammonium ion (TPA) and silica sol isin a range of 0.015 to 0.08 by mole, the average particle diameter ofthe zeolite shaped body is not changed and the bending strength is 1.5MPa or higher, which is required for a substrate to be used forproduction of a zeolite layered composite, (the strength high enough toavoid the damage of a zeolite membrane in hydrothermal synthesisenvironments and the damage even after membrane formation.) and forthat, the mixing ratio maybe adjustable within said range. The rawmaterials of tetrapropylammonium ion (TPA) may be a tetrapropylammoniumhydroxide (TPAOH) solution, tetrapropylammonium bromide (TPABr), or amixture of these two raw materials. If the mole ratio of TPA/SiO₂ iskept in prescribed value in said produced solution, an alkaline sourcesuch as sodium hydroxide, potassium hydroxide, and the like may be addedto adjust pH, if necessary.

[0147] In the examples of the third invention, the TPA/SiO₂ mole ratiois adjusted to be 0.04 at which the bending strength becomes the maximumand as a tetrapropylammonium ion (TPA) source, a tetrapropylammoniumhydroxide (TPAOH) solution is used to produce the solution.

[0148] Then, in order to dry the produced solution once, the producedsolution is added to a Teflon beaker and stirred by a magnetic stirrerand then, while being heated in a thermostat at a prescribedtemperature, the solution is continuously manually stirred with a Teflonrod and kneaded to evaporate water and obtain a dried gel. The stirringand kneading in this case may be carried out using a heating kneader orthe like.

[0149] Then, in order to produce a slurry of the dried gel, the driedgel obtained by stirring and kneading, distilled water, and ball forpulverization are added to a Teflon container to carry out wet ball millpulverization. At this time, other than the wet ball mill pulverization,for example, the dried gel may finely be pulverized by a medium stirringand pulverizing apparatus (an attriter) and then mixed with a prescribedamount of distilled water to produce a slurry.

[0150] Then, the slurry is sprayed and dried by the spraying method asdescribed above to obtain a dried gel granulated product.

[0151] Then, the dried gel granulated product is shaped by properlyforming the product in a prescribed shape by a uniaxial pressing with adie (the total pressure 1,000 kgf) and then carrying out cold isostaticpressing to obtain a dried gel shaped body. At this time, the pressureof the cold isostatic pressing is preferable to be adjusted within arange of 700 to 7,000 kgf/cm² so as to make the resulting dried gelshaped body to have a desired density.

[0152] Then, the dried gel shaped body obtained in the manner asdescribed above is put on a Teflon plate so as to keep the shaped bodyfrom water in a Teflon inner cylinder-attached pressure vessel made of astainless steel and storing distilled water in the same weight as thatof the shaped body and reaction is caused under spontaneous steampressure for 10 hours in an oven at 180° C. and crystallization iscarried out to obtain a zeolite shaped body. The amount of the distilledwater at this time is the minimum level of the amount with which thesteam pressure reaches the saturated pressure for the volume of thepressure vessel used and if the amount is that level or higher, there isno particular restriction in terms of the relation of a shaped body anddistilled water. Further, regarding the reaction temperature and time,since crystallization proceeds at 130° C. or higher for 2 hours orlonger, the temperature and the time are not particularly restricted ifthey are the above mentioned levels or more, respectively.

[0153] Further, the zeolite shaped body production method of the thirdinvention may comprises processes of adding a tetrapropylammoniumhydroxide (TPAOH) solution to silica sol in such a manner that the moleratio of mixing ratio (TPA/SiO₂ mole ratio) of tetrapropylammonium ion(TPA) and the silica sol becomes a range of 0.015 to 0.08, spraying thusobtained solution to dry, shaping the obtained dried gel, and subjectingthus shaped gel to crystallization treatment.

[0154] More practically, at first, silica sol and a tetrapropylammoniumhydroxide (TPAOH) solution are mixed. At this time, if the mixing ratio(TPA/SiO₂ by mole ratio) of tetrapropylammonium ion (TPA) and silica solis in a range of 0.015 to 0.08 by mole, preferably in a range of 0.02 to0.06 by mole, the average particle diameter of the zeolite shaped bodyis not changed and the bending strength is 1.5 MPa or higher, which isrequired for a substrate to be used for production of a zeolite layeredcomposite, and for that, the mixing ratio may be adjustable within abovedescribed any range. The raw materials of tetrapropylammonium ion (TPA)may be a tetrapropylammonium hydroxide (TPAOH) solution,tetrapropylammonium bromide (TPABr), or a mixture of these two rawmaterials. Further, if the mole ratio of TPA/SiO₂ is kept in prescribedvalue in said produced solution, an alkaline source such as sodiumhydroxide, potassium hydroxide, and the like may be added to adjust pH,if necessary.

[0155] Incidentally, in the examples of the third invention, theTPA/SiO₂ mole ratio is adjusted to be 0.04 at which the bending strengthbecomes the maximum and as a tetrapropylammonium ion (TPA) source, atetrapropylammonium hydroxide (TPAOH) solution is used to produced thesolution.

[0156] Then, said solution is sprayed and dried by the spraying methodas described above to obtain a dried gel.

[0157] Then, the dried gel is shaped by properly forming the product ina prescribed shape by a uniaxial pressing with a die (the total pressure1,000 kgf) and then carrying out cold isostatic pressing to obtain adried gel shaped body. At this time, the pressure of the cold isostaticpressing is preferable to be adjusted within a range of 700 to 7,000kgf/cm² so as to make the resulting dried gel shaped body to have adesired density.

[0158] Then, the dried gel shaped body obtained in the manner asdescribed above is put on a Teflon plate so as to keep the shaped bodyfrom water in a Teflon inner cylinder-attached pressure vessel made of astainless steel and storing distilled water in the same weight as thatof the shaped body and reaction is caused under spontaneous steampressure for 10 hours in an oven at 180° C. and crystallization iscarried out to obtain a zeolite shaped body. The amount of the distilledwater at this time is the minimum level of the amount with which thesteam pressure reaches the saturated pressure for the volume of thepressure vessel used and if the amount is that level or higher, there isno particular restriction in terms of the relation of a shaped body anddistilled water. Further, regarding the reaction temperature and time,since crystallization proceeds at 130° C. or higher for 2 hours orlonger, the temperature and the time are not particularly restricted ifthey are the above mentioned levels or more, respectively.

[0159] The method for drying by spraying in such a manner can carry outdrying more homogeneously and prevent the microstructure after thecrystallization treatment more efficiently from being coarsened anddegranulated than a conventional method for drying by kneading.

[0160] A zeolite layered intermediate body of the third invention ischaracterized by comprising a zeolite shaped body and atemplate-containing zeolite having the composition same as or similar tothat of the shaped body and formed on the shaped body.

[0161] The formation method of the template-containing zeolite is notparticularly restricted, and applicable are, for example, a hydrothermalsynthesis method and a vapor phase transport method and the like.

[0162] Further, a zeolite layered composite of the third invention ischaracterized by comprising a zeolite shaped body and a zeolite membraneformed thereon and being produced by removing the template from saidzeolite shaped body and said template-containing zeolite membrane bycalcining said zeolite layered intermediate body.

[0163] In this case, since said zeolite layered composite is to beemployed effectively for a gas separation membrane of a molecular sievemembrane and a pervaporation membrane, a template-containing zeolitemembrane or a zeolite membrane, from which the template is removed, tobe layered on a zeolite shaped body is required to have sufficientthickness so as to prevent exposure of the zeolite shaped body and to bea dense membrane. Further, in the case where those containing a templateare used as a zeolite shaped body, a template-containing zeolitemembrane to be layered thereon is required to be made of a zeolite withthe composition same as or similar to that of the zeolite shaped body,including that the membrane contains the same template.

[0164] A zeolite layered intermediate body production method of thethird invention is characterized by comprising the processes of adding atetrapropylammonium hydroxide (TPAOH) solution to silica sol in such amanner that the mole ratio of mixing ratio (TPA/SiO₂) oftetrapropylammonium ion (TPA) and the silica sol becomes 0.015 to 0.08,drying the produced solution by kneading the solution, wet pulverizingthe obtained dried gel, spraying thus obtained slurry to dry, shapingthe obtained dried gel, subjecting thus shaped gel to crystallizationtreatment to obtain a zeolite shaped body, immersing the obtainedzeolite shaped body in a solution having the same as or similarcomposition to that of the prepared solution, and forming atemplate-containing zeolite membrane on the zeolite shaped body byhydrothermally synthesizing it thereon to produce a layered bodycomprising the zeolite shaped body and the template-containing zeolitemembrane. More practical description will be given in the description ofa zeolite layered composite production method of the third invention.

[0165] Further, the method maybe a method characterized by comprisingthe processes of adding a tetrapropylammonium hydroxide (TPAOH) solutionto silica sol in such a manner that the mole ratio of mixing ratio(TPA/SiO₂) of tetrapropylammonium ion (TPA) and the silica sol becomes0.015 to 0.08, spraying thus prepared solution to dry, shaping the driedgel, subjecting the shaped product to crystallization treatment toobtain a zeolite shaped body, immersing the obtained zeolite shaped bodyin a solution with the same or similar composition as or to that of thesolution, and forming a template-containing zeolite membrane on thezeolite shaped body by hydrothermally synthesizing it thereon to producea layered body comprising the zeolite shaped body and thetemplate-containing zeolite membrane. It will be described in thedescription of a zeolite layered composite production method of thethird invention.

[0166] A zeolite layered composite production method of the thirdinvention is characterized by comprising the processes of adding atetrapropylammonium hydroxide (TPAOH) solution to silica sol in such amanner that the mole ratio of mixing ratio (TPA/SiO₂) oftetrapropylammonium ion (TPA) and the silica sol becomes 0.015 to 0.08,drying thus prepared solution by kneading the solution, wet pulverizingthe obtained dried gel, drying the obtained slurry by spraying, shapingthe obtained dried granulated product, subjecting the shaped gel tocrystallization treatment to obtain a zeolite shaped body, immersing theobtained zeolite shaped body in a solution having the same or similarcomposition as or to that of the prepared solution, forming atemplate-containing zeolite membrane on the zeolite shaped body byhydrothermally synthesizing it thereon to produce a layered bodycomprising the zeolite shaped body and the template-containing zeolitemembrane, and then simultaneously removing the template by calcining thelayered body.

[0167] More practically, at first, silica sol and a tetrapropylammoniumhydroxide (TPAOH) solution are mixed. At this time, if the mixing ratio(TPA/SiO₂ mole ratio) of tetrapropylammonium hydroxide (TPAOH) andsilica sol is in a range of 0.015 to 0.08 by mole, preferably 0.02 to0.06, the average particle diameter of the zeolite shaped body is notchanged and the bending strength is 1.5 MPa or higher, which is requiredfor a substrate to be used for production of a zeolite layered compositeand for that, the mixing ratio may be adjustable within said any rangeof mole ratio. The raw materials of tetrapropylammonium ion (TPA) may bea tetrapropylammonium hydroxide (TPAOH) solution, tetrapropylammoniumbromide (TPABr), or a mixture of these two raw materials. If the moleratio of TPA/SiO₂ is kept in prescribed value in the produced solution,an alkaline source such as sodium hydroxide, potassium hydroxide, andthe like may be added to adjust pH, if necessary.

[0168] In the examples of the third invention, the TPA/SiO₂ mole ratiois adjusted to be 0.04 at which the bending strength becomes the maximumand as a tetrapropylammonium ion (TPA) source, a tetrapropylammoniumhydroxide (TPAOH) solution is used to produced the solution.

[0169] Then, in order to dry the produced solution once, the producedsolution is added to a Teflon beaker and stirred by a magnetic stirrerand then, while being heated in a thermostat at a prescribedtemperature, the solution is continuously manually stirred using aTeflon rod and kneaded to evaporate water and obtain a dried gel. Thestirring and kneading in this case may be carried out using a heatingkneader or the like.

[0170] Then, in order to produce a slurry of the dried gel, the driedgel, distilled water, and ball for pulverization are added to a Tefloncontainer to carry out wet ball mill pulverization. At this time, otherthan the wet ball mill pulverization, for example, the dried gel mayfinely be pulverized by a medium stirring and pulverizing apparatus (anattriter) and then mixed with a prescribed amount of distilled water toproduce a slurry.

[0171] Then, the slurry is sprayed and dried by the spraying method asdescribed above to obtain a dried gel granulated product.

[0172] Then, the dried gel granulated product is shaped by properlyforming the product in a prescribed shape by a uniaxial pressing with adie (the total pressure 1,000 kgf) and then carrying out cold isostaticpressing to obtain a dried gel shaped body. At this time, the pressureof the cold isostatic pressing is preferable to be adjusted within arange of 700 to 7,000 kgf/cm² so as to make the resulting dried gelshaped body to have a desired density.

[0173] Then, the dried gel shaped body obtained in the manner asdescribed above is put on a Teflon plate so as to keep the shaped bodyfrom water in a Teflon inner cylinder-attached pressure vessel made of astainless steel and storing distilled water in the same weight as thatof the shaped body and reaction is caused under spontaneous steampressure for 10 hours in an oven at 180° C. and crystallization iscarried out to obtain a zeolite shaped body. The amount of the distilledwater at this time is the minimum level of the amount with which thesteam pressure reaches the saturated pressure for the volume of thepressure vessel used and if the amount is that level or higher, there isno particular restriction in terms of the relation of a shaped body anddistilled water. Further, regarding the reaction temperature and time,since crystallization proceeds at 130° C. or higher for 2 hours orlonger, the temperature and the time are not particularly restricted ifthey are the above mentioned levels or more, respectively.

[0174] Layering a zeolite membrane on the zeolite shaped body obtainedin such a manner is carried out as follows.

[0175] A zeolite layered composite is obtained by adding a TPAOHsolution, TPABr, and distilled water to silica sol in such a manner thatthe mole ratio of SiO₂/TPAOH/TPABr/water becomes a prescribed value toprepare a mixed solution, charging the obtained solution to a pressurevessel, immersing a zeolite shaped body in the prepared solution,causing reaction for 1 hour or longer in an oven at 100° C. or higher toform a sufficiently thick and dense layer of a template-containingzeolite membrane on the zeolite shaped body and to obtain a zeolitelayered intermediate body, and calcining the zeolite layeredintermediate body. In the examples of the third invention, reaction iscarried out for 18 hours in an oven at 180° C. to form a dense layer ofa zeolite membrane with the thickness of 20 μm or thicker on the zeoliteshaped body.

[0176] Incidentally, if the mole ratio of SiO₂/tetrapropylammonium ion(TPA)/water is kept in prescribed value, an alkaline source such assodium hydroxide, potassium hydroxide, and the like may be added toadjust pH, if necessary.

[0177] The zeolite layered composite production method of the thirdinvention may comprise processs of adding a tetrapropylammoniumhydroxide (TPAOH) solution to silica sol in such a manner that the moleratio of mixing ratio (TPA/SiO₂) of tetrapropylammonium ion (TPA) to thesilica sol becomes 0.015 to 0.08, preferably 0.02 to 0.06, spraying thusprepared solution to dry, shaping the obtained dried gel, and subjectingthus shaped product to crystallization treatment to obtain a zeoliteshaped body, immersing the obtained zeolite shaped body in a solutionwith the same or similar composition as or to that of the solution,forming a template-containing zeolite membrane on the zeolite shapedbody by hydrothermally synthesizing it thereon to produce a layered bodycomprising the zeolite shaped body and the template-containing zeolitemembrane, and simultaneously removing the template by calcining theobtained layered body.

[0178] More practically, at first, silica sol and a tetrapropylammoniumhydroxide (TPAOH) solution are mixed. At this time, if the mixing ratio(TPA/SiO₂ mole ratio) of tetrapropylammonium hydroxide (TPAOH) andsilica sol is in a range of 0.015 to 0.08 by mole, the average particlediameter of the zeolite shaped body is not changed and the bendingstrength is 1.5 MPa or higher, which is required for a substrate to beused for production of a zeolite layered composite, and for that, themixing ratio may be adjustable within said range. Further, the rawmaterials of tetrapropylammonium ion (TPA) maybe a tetrapropylammoniumhydroxide (TPAOH) solution, tetrapropylammonium bromide (TPABr), or amixture of these two raw materials. If the mole ratio of TPA/SiO₂ iskept in prescribed value in the produced solution, an alkaline sourcesuch as sodium hydroxide, potassium hydroxide, and the like may be addedto adjust pH, if necessary.

[0179] In the examples of the third invention, the TPA/SiO₂ mole ratiois adjusted to be 0.04 at which the bending strength becomes the maximumand as a tetrapropylammonium ion (TPA) source, a tetrapropylammoniumhydroxide (TPAOH) solution is used to produced the solution.

[0180] Then, the produced solution is sprayed and dried by the sprayingmethod as described above to obtain a dried gel.

[0181] Then, the dried gel is shaped by properly forming the dried gelin a prescribed shape by a uniaxial pressing with a die (the totalpressure 1,000 kgf) and then carrying out cold isostatic pressing toobtain a dried gel shaped body. At this time, the pressure of the coldisostatic pressing is preferable to be adjusted within a range of 700 to7,000 kgf/cm so as to make the resulting dried gel shaped body to have adesired density.

[0182] Then, the dried gel shaped body obtained in the manner asdescribed above is put on a Teflon plate so as to keep the shaped bodyfrom water in a Teflon inner cylinder-attached pressure vessel made of astainless steel and storing distilled water in the same weight as thatof the shaped body and reaction is caused under spontaneous steampressure for 10 hours in an oven at 180° C. and crystallization iscarried out to obtain a zeolite shaped body. The amount of the distilledwater at this time is the minimum level of the amount with which thesteam pressure reaches the saturated pressure for the volume of thepressure vessel used and if the amount is that level or higher, there isno particular restriction in terms of the relation of a shaped body anddistilled water. Further, regarding the reaction temperature and time,since crystallization proceeds at 130° C. or higher for 2 hours orlonger, the temperature and the time are not particularly restricted ifthey are the above mentioned levels or more, respectively.

[0183] Layering a zeolite membrane on the zeolite shaped body obtainedin such a manner is carried out as follows.

[0184] A zeolite layered composite is obtained by adding a TPAOHsolution, TPABr, and distilled water to silica sol in such a manner thatthe mole ratio of SiO₂/TPAOH/TPABr/water becomes a prescribed value toprepare a mixed solution, charging the obtained solution to a pressurevessel, immersing a zeolite shaped body in the prepared solution,causing reaction for 1 hour or longer in an oven at 100° C. or higher toform a sufficiently thick and dense layer of a template-containingzeolite membrane on the zeolite shaped body and to obtain a zeolitelayered intermediate body, and calcining the zeolite layeredintermediate body. In the examples of the third invention, reaction iscarried out for 18 hours in an oven at 180° C. to form a dense layer ofa zeolite membrane with the thickness of 20 μm or thicker on the zeoliteshaped body.

[0185] Incidentally, if the mole ratio of SiO₂/tetrapropylammonium ion(TPA)/water is kept in prescribed value, an alkaline source such assodium hydroxide, potassium hydroxide, and the like may be added toadjust pH, if necessary.

[0186] Incidentally, as a method zeolite layered composite productionmethod of the third invention, same method as those in the case of thefirst invention and the second invention may be employed.

[0187] Hereinafter, the present invention will more practically bedescribed according to the examples, however the invention is not at allrestricted to those examples.

EXAMPLES 1 to 5, COMPARATIVE EXAMPLES 1 to 7 The First Invention (1)

[0188] A Teflon beaker of 200 ml capacity was charged with about 30% byweight of silica sol (trade name: Snowtex S, produced by CorporationNissan Chemical) and a 10% tetrapropylammonium hydroxide solution(produced by Wako Pure Chemical Industries, Ltd.) and the mixing ratio(TPA/SiO₂) of TPA (tetrapropylammonium ion) and SiO₂ was separatelyadjusted as shown in Table 1 in mole ratio and the resulting eachsolution was stirred at room temperature for 30 minutes by a magneticstirrer and after that, while being heating at 80° C., each solution wascontinuously stirred and kneaded to evaporate water and to obtain acolorless dried gel with 10% by weight or lower water content. Theobtained each dried gel was subjected to x-ray diffraction toinvestigate the crystal structure to find it was amorphous.

[0189] The obtained each dried gel was pulverized in an agate crucibleand passed through meshes of 355 μm to obtain an under-mesh powder andafter that, each powder was pressed by a uniaxial pressing with a die atthe entire pressure of 1 t to separately obtain a rod-like shaped bodyof 4 mm×4 mm×50 mm.

[0190] The obtained each shaped body was set on a Teflon plate so as tokeep each shaped body from water in a Teflon inner cylinder-attachedpressure vessel made of a stainless steel and filled with distilledwater in a half of the weight of the shaped body and reaction was causedunder spontaneous steam pressure for 18 hours in an oven at 180° C. andcrystallization is carried out to obtain each zeolite shaped body.

[0191] Respective zeolite shaped bodies obtained in the examples 1 to 5and the comparative examples 1 to 7 were subjected to x-ray diffractionto investigate their crystal phase and find that they were porous bodiesof a MFI type zeolite and that the zeolite was completely crystallizedin terms of x-ray investigation. Incidentally, the one obtained in thecomparative example 1 was not a zeolite.

[0192] Then, after being sufficiently dried at 80° C., the respectivezeolite shaped bodies obtained in the examples 1 to 5 and thecomparative examples 1 to 7 were subjected to 4-point bending strengthmeasurement according to JIS R1601. The results are shown in Table 1.TABLE 1 TPA/SiO₂ 4-point bending strength (mole ratio) (MPa) Example 10.015 3.7 Example 2 0.020 13.6 Example 3 0.040 15.7 Example 4 0.060 8.6Example 5 0.080 5.2 Comparative example 1 0.000 — Comparative example 20.005 0.5 Comparative example 3 0.010 0.6 Comparative example 4 0.1001.4 Comparative example 5 0.120 0.9 Comparative example 6 0.140 0.4Comparative example 7 0.200 0.2

[0193] According to Table 1, the zeolite shaped bodies of completelycrystallized zeolites as those of the examples 1 to 5 were found havingthe strength of 3 MPa or higher by adjusting the mixing ratio (TPA/SiO₂)of TPA (tetrapropylammonium ion) and SiO₂ to be 0.015 to 0.08 by mole.

EXAMPLES 6 to 11, COMPARATIVE EXAMPLES 8 to 10 The First Invention (2)

[0194] A Teflon beaker of 200 ml capacity was charged with about 30% 10by weight of silica sol (trade name: Snowtex S, produced by CorporationNissan Chemical) and a 10% tetrapropylammonium hydroxide solution(produced by Wako Pure Chemical Industries, Ltd.) and the mixing ratio(TPA/SiO₂) of TPA (tetrapropylammonium ion) and SiO₂ was separatelyadjusted as shown in Table 2 [in mole ratio] and the resulting eachsolution was stirred at room temperature for 30 minutes by a magneticstirrer and after that, while being heating at 80° C., each solution wasfurther continuously stirred and kneaded to evaporate water and toobtain a colorless dried gel with 10% by weight or lower water content.The obtained each dried gel was subjected to x-ray diffraction toinvestigate the crystal structure to find it was amorphous.

[0195] The obtained each dried gel was pulverized in an agate crucibleand passed through meshes of 355 μm to obtain an under-mesh powder andafter that, each powder was pressed by a uniaxial press with a die atthe entire pressure of 1 t to separately obtain a rod-like shaped bodyof 4 mm×4 mm×50 mm.

[0196] The obtained each shaped body was set on a Teflon plate so as tokeep each shaped body from water in a Teflon inner cylinder-attachedpressure vessel made of a stainless steel and filled with distilledwater in a half of the weight of the shaped body and reaction was causedunder spontaneous steam pressure for 10 hours in an oven at 130° C. andcrystallization is carried out to obtain each zeolite shaped body.

[0197] Respective zeolite shaped bodies obtained in the examples 6 to 11and the comparative examples 8 to 10 were subjected to x-ray diffractionto investigate their crystal phase and find that those obtained in thecomparative examples 9 to 10 were porous bodies of a MFI type zeoliteand that those obtained in the examples 6 to 11 were porous zeolitebodies still under crystalization comprising a MFI type zeolite andamorphous zeolite. Incidentally, the one obtained in the comparativeexample 8 was not a zeolite.

[0198] Then, after being sufficiently dried at 80° C., the respectivezeolite shaped body obtained in the examples 6 to 11 and the comparativeexamples 8 to 10 were subjected to 4-point bending strength measurementaccording to JIS R1601. The results are shown in Table 2. TABLE 2TPA/SiO₂ 4-point bending strength (mole ratio) (MPa) Example 6 0.02 1.8Example 7 0.04 5.7 Example 8 0.06 14.1 Example 9 0.08 13.2 Example 100.10 4.7 Example 11 0.12 2.3 Comparative example 8 0.00 — Comparativeexample 9 0.14 1.2 Comparative example 10 0.20 0.2

[0199] According to Table 2, the zeolite shaped bodies of zeolites stillunder crystallization as those of the examples 6 to 11 were found havingthe strength of 1.5 MPa or higher by adjusting the mole ratio (TPA/SiO₂)of TPA (tetrapropylammonium ion) and SiO₂ to be 0.02 to 0.12.

EXAMPLE 12 The First Invention (3)

[0200] A sol for membrane formation was produced by mixing 15.26 g of a10% tetrapropylammonium hydroxide solution (produced by Wako PureChemical Industries, Ltd.) and 2.00 g of tetrapropylammonium bromide(produced by Wako Pure Chemical Industries, Ltd.), further adding 49.85g of distilled water, and 6.00 g of about 30% by weight of silica sol(trade name: Snowtex S, produced by Corporation Nissan Chemical), andstirring the resulting mixture at room temperature for 30 minutes by amagnetic stirrer.

[0201] The resulting sol was added to a Teflon inner cylinder-attachedpressure vessel with 100 ml capacity made of a stainless steel and thezeolite shaped body obtained in the example 3 was immersed in the soland reacted for 18 hours in an oven at 180° C. Observation of thefractured surface by a scanning electron microscope (SEM) after thereaction made it clear that an about 17 μm thick dense layer was formedon the porous zeolite shaped body as shown in the scanning electronmicroscope (SEM) photograph of FIG. 1 and it was found by x-raydiffraction that the dense membrane was of a MFI type zeolite membrane.

[0202] When the zeolite layered intermediate body obtained as describedabove was heated to 500° C. and kept at the temperature for 4 hours inan electric furnace to remove tetrapropylammonium, no crack was observedby a Rhodamine test, which will be described later, and no molecule wasfound permeating by a pervaporation method using triethylbenzene to makeit clear that a dense zeolite membrane free of cracks was formed.

EXAMPLE 13 The First Invention (4)

[0203] The zeolite shaped body obtained in example 7 was immersed in thesol similar to that of the example 12 and added to a Teflon innercylinder-attached pressure vessel with 100 ml capacity made of astainless steel and reacted for 18 hours in an oven at 180° C.Observation of the fractured surface by SEM after the reaction made itclear that a dense layer similar to that in the example 3 was formed onthe porous zeolite shaped body and it was found by x-ray diffractionthat the dense membrane was of a MFI type zeolite membrane. Further, theparts of the shaped body which were amorphous before the membraneformation were converted into the MFI type zeolite by the membraneformation to obtain a zeolite layered intermediate body comprising thezeolite shaped body and a zeolite membrane formed thereon.

[0204] When the zeolite layered intermediate body obtained as describedabove was heated to 500° C. and kept at the temperature for 4 hours inan electric furnace to remove tetrapropylammonium, as shown in Table 3,no crack was observed by a Rhodamine test and no molecule was foundpermeating by a pervaporation method using triisopropylbenzene (TIPB) tomake it clear that a dense zeolite membrane free of cracks was formed.

COMPARATIVE EXAMPLE 11 The First Invention (5)

[0205] A porous aluminum was immersed in the sol produced in the samemanner as the example 12 and a zeolite membrane was formed in the samemanner as the example 12.

[0206] When the resulting membrane was heated to 500° C. and kept at thetemperature for 4 hours in an electric furnace to removetetrapropylammonium, as shown in Table 3, cracks were observed by aRhodamine test described later and molecules were found permeating by apervaporation method using triisopropylbenzene to make it clear that themembrane was not a gas tight membrane.

COMPARATIVE EXAMPLE 12 The First Invention (6)

[0207] A porous silicon nitride was immersed in the sol produced in thesame manner as the example 12 and a zeolite membrane was formed in thesame manner as the example 12.

[0208] When the resulting membrane was heated to 500° C. and kept at thetemperature for 4 hours in an electric furnace to removetetrapropylammonium, as shown in Table 3, cracks were observed by aRhodamine test described later and molecules were found permeating by apervaporation method using triisopropylbenzene to make it clear that themembrane was not a gas tight membrane.

COMPARATIVE EXAMPLE 13 The First Invention (7)

[0209] A porous mullite was immersed in the sol produced in the samemanner as the example 12 and a zeolite membrane was formed in the samemanner as the example 12.

[0210] When the resulting membrane was heated to 500° C. and kept at thetemperature for 4 hours in an electric furnace to removetetrapropylammonium, as shown in Table 3, cracks were observed by aRhodamine test described later and molecules were found permeating by apervaporation method using triisopropylbenzene to make it clear that themembrane was not a gas tight membrane.

COMPARATIVE EXAMPLE 14 The First Invention (8)

[0211] A porous silica glass was immersed in the sol produced in thesame manner as the example 12 and a zeolite membrane was formed in thesame manner as the example 12.

[0212] When the resulting membrane was heated to 500° C. and kept at thetemperature for 4 hours in an electric furnace to removetetrapropylammonium, as shown in Table 3, cracks were observed by aRhodamine test described later and molecules were found permeating by apervaporation method using triisopropylbenzene to make it clear that themembrane was not a gas tight membrane.

COMPARATIVE EXAMPLE 15 The First Invention (9)

[0213] A porous cordierite was immersed in the sol produced in the samemanner as the example 12 and a zeolite membrane was formed in the samemanner as the example 12.

[0214] When the resulting membrane was heated to 500° C. and kept at thetemperature for 4 hours in an electric furnace to removetetrapropylammonium, as shown in Table 3, cracks were observed by aRhodamine test described later and molecules were found permeating by apervaporation method using triisopropylbenzene to make it clear that themembrane was not a gas tight membrane. TABLE 3 Compara- Compara-Compara- Compara- Compara- tive tive tive tive tive Example Exampleexample example example example example 12 13 11 12 13 14 15 Cracks NoneNone Observed Observed Observed Observed Observed TIPB Imperme- Imperme-Perme- Perme- Perme- Perme- Perme- molecule able able able able ableable able

EXAMPLES 14 to 18 The Second Invention (1)

[0215] A Teflon beaker of 200 ml capacity was charged with about 30% byweight of silica sol (trade name: Snowtex S, produced by CorporationNissan Chemical), a 10% tetrapropylammonium hydroxide solution (producedby Wako Pure Chemical Industries, Ltd.), and tetrapropylammonium bromide(TPABr) (produced by Wako Pure Chemical Industries, Ltd.) while themixing ratio (TPA/SiO₂) of TPA (tetrapropylammonium ion) and silica solbeing adjusted to be 0.04 by mole and the respective mixing ratios[TPAOH/(TPAOH+TPABr) and TPABr/(TPAOH+TPABr)] of tetrapropylammoniumhydroxide (TPAOH) and tetrapropylammonium bromide (TPABr) to the totalamount of tetrapropylammonium ion (TPA) being separately adjusted asshown in Table 4 in mole %, and further sodium hydroxide in the sameamount (by mole) as the addition amount (by mole) of tetrapropylammoniumbromide (TPABr) was added in the form of an aqueous solution of about 2%by weight of sodium hydroxide and the resulting each solution wasstirred at room temperature for 30 minutes by a magnetic stirrer andafter that, while being heating at 80° C., each solution wascontinuously stirred and kneaded manually using a Teflon rod toevaporate water and to obtain a colorless dried gel. The obtained eachdried gel was subjected to x-ray diffraction to investigate the crystalstructure to find it was amorphous.

[0216] The obtained each dried gel was pulverized in an agate crucibleand passed through meshes of 355 μm to obtain an under-mesh powder andafter that, each powder was pressed by a uniaxial press with a die (theentire pressure of 1,000 kgf) to obtain a rod-like shaped body of 5×4×40mm and a disk-like shaped body of 18 mmφ diameter and 1.8 mm thicknessand further shaped by cold isostatic pressing (the entire pressure of2,500 kgf/cm² to obtain shaped bodies. The obtained each shaped body wasset on a Teflon plate so as to keep each shaped body from water in aTeflon inner cylinder-attached pressure vessel of 100 ml capacity madeof a stainless steel and filled with distilled water in the same weightas that of each shaped body and reaction was caused under spontaneoussteam pressure for 10 hours in an oven at 180° C. Shaped bodies wereinvestigated by x-ray diffraction after the reaction to be found all oftheir compositions were MFI type zeolites. The shaped bodies weresufficiently dried at 80° C. to obtain zeolite shaped bodies.

[0217] The microstructure of the fractured surface of each zeoliteshaped body obtained in such a manner as described above was observed bya scanning electron microscope (SEM) as described above and according tothe photograph, the average particle diameter was calculated to find, asshown in Table 4 and FIG. 3, that as the mixing ratio[TPABr/(TPAOH+TPABr)] of tetrapropylammonium bromide (TPABr) to thetotal amount of tetrapropylammonium ion (TPA) was increased to 5, 12.5,25, 37.5, and 50% by mole, the average particle diameter was increasedto 1.5, 2.7, 6.4, 8.8, and 13.9 μm.

[0218] The scanning electron microscope (SEM) photographs of theexamples 14 to 18 are shown in FIG. 4 to FIG. 8, respectively.

[0219] Then, the rod-like respective zeolite shaped bodies weresubjected to 4-point bending strength measurement according to JIS R1601to find, as shown in Table 4 and FIG. 9, that as the mixing ratio[TPABr/(TPAOH+TPABr)] of tetrapropylammonium bromide (TPABr) to thetotal amount of tetrapropylammonium ion (TPA) was increased to 5, 12.5,25, 37.5, and 50% by mole, the bending strength was decreased and also,as shown in FIG. 10, that as the average particle diameter wasincreased, the bending strength was decreased.

[0220] Further, the disk-like respective zeolite shaped bodies weresubjected to pressure loss measurement to find, as shown in Table 4,that as the mixing ratio [TPABr/(TPAOH+TPABr)] of tetrapropylammoniumbromide (TPABr) to the total amount of tetrapropylammonium ion (TPA) wasincreased to 5, 12.5, 25, 37.5, and 50% by mole, the pressure loss wasdecreased and also, as shown in FIG. 11, that as the average particlediameter was increased, the pressure loss was decreased.

EXAMPLE 19 The Second Invention (2)

[0221] A Teflon beaker of 200 ml capacity was charged with about 30% byweight of silica sol (trade name: Snowtex S, produced by CorporationNissan Chemical) and tetrapropylammonium bromide (TPABr) (produced byWako Pure Chemical Industries, Ltd.) while the mixing ratio (TPA/SiO₂)of TPA (tetrapropylammonium ion) of TPABr and silica sol being adjustedto be 0.04 by mole ratio and further sodium hydroxide in the same amount(by mole) as the addition amount (by mole) of tetrapropylammoniumbromide (TPABr) was added in the form of an aqueous solution of about 2%by weight of sodium hydroxide and the resulting solution was stirred atroom temperature for 30 minutes by a magnetic stirrer and after that,while being heating at 80° C., the solution was continuously stirred andkneaded manually using a Teflon rod to evaporate water and to obtain acolorless dried gel. The obtained dried gel was subjected to x-raydiffraction to investigate the crystal structure to find it wasamorphous.

[0222] The obtained dried gel was processed in the same manner as in thecase of the examples 14 to 18 to obtain each zeolite shaped body.

[0223] The microstructure of the fractured surface of each zeoliteshaped body was observed by a scanning electron microscope (SEM) in thesame manner as described above in the examples 14 to 18, and accordingto the photograph, the average particle diameter was calculated to findthe average particle diameter was 24 μm (reference to FIG. 3). Thescanning electron microscope (SEM) photograph is shown in FIG. 12.

[0224] Further, the rod-like zeolite shaped body was subjected to4-point bending strength measurement in the same manner as the examples14 to 18 to find, as shown in Table 4, FIG. 9, and FIG. 10, it was 2MPa.

[0225] Further, the disk-like zeolite shaped body was subjected topressure loss measurement in the same manner as the examples 14 to 18 tofind, as shown in Table 4 and FIG. 11, it was 0.3×10⁻³ atmosphericpressure.

EXAMPLE 20 The Second Invention (3)

[0226] A Teflon beaker of 200 ml capacity was charged with about 30% byweight of silica sol (trade name: Snowtex S, produced by CorporationNissan Chemical) and a 10% tetrapropylammonium hydroxide (TPAOH)solution (produced by Wako Pure Chemical Industries, Ltd.) while themixing ratio (TPA/SiO₂) of TPA (tetrapropylammonium ion) of the TPAOHsolution and silica sol being adjusted to be 0.04 by mole ratio and theresulting solution was stirred at room temperature for 30 minutes by amagnetic stirrer to obtain a mixed solution of tetrapropylammoniumhydroxide (TPAOH) and silica sol for a spray drier. The mixed solutionwas dried by a spray drier apparatus (trade name: Valvis Mini Spray GA32 model manufactured by Yamato Science Co., Ltd.) in conditions of 1kgf/cm² spraying air pressure, 0.4 m³/min dried air flow rate, 3 ml/minsolution feeding rate, and 180° C. blowing temperature to obtain a driedgel. The obtained dried gel was subjected to x-ray diffraction toinvestigate the crystal structure to find it was amorphous.

[0227] The obtained dried gel was processed in the same manner as in thecase of the examples 14 to 18 to obtain each zeolite shaped body.

[0228] The microstructure of the fractured surface of each zeoliteshaped body was observed by a scanning electron microscope (SEM) in thesame manner as described above in the examples 14 to 18 to find themicrostructure was free of defects and a homogeneous structure withoutshowing non-denseness and denseness in the granule. According to thephotograph, the average particle diameter was calculated to find theaverage particle diameter was 7.5 μm. The scanning electron microscope(SEM) photograph is shown in FIG. 13.

[0229] Further, the rod-like zeolite shaped body was subjected to4-point bending strength measurement in the same manner as the examples14 to 18 to find, as shown in Table 4, it was 6 MPa. Further, as shownin Table 4 and FIG. 11, the disk-like zeolite shaped body was subjectedto pressure loss measurement in the same manner as the examples 14 to 18to find it was 0.6×10⁻³ atmospheric pressure.

COMPARATIVE EXAMPLE 16 The Second Invention (4)

[0230] A Teflon beaker of 200 ml capacity was charged with about 30% byweight of silica sol (trade name: Snowtex S, produced by CorporationNissan Chemical) and a 10% tetrapropylammonium hydroxide (TPAOH)solution (produced by Wako Pure Chemical Industries, Ltd.) while themixing ratio (TPA/SiO₂) of TPA (tetrapropylammonium ion) of the TPAOHsolution and silica sol being adjusted to be 0.04 by mole and theresulting solution was stirred at room temperature for 30 minutes by amagnetic stirrer and after that, while being heated at 80° C., thesolution was further continuously stirred and kneaded manually by aTeflon rod to evaporate water and obtain a colorless dried gel. Theobtained dried gel was subjected to x-ray diffraction to investigate thecrystal structure to find it was amorphous.

[0231] The obtained dried gel was processed in the same manner as in thecase of the examples 14 to 18 to obtain each zeolite shaped body.

[0232] The microstructure of the fractured surface of each zeoliteshaped body was observed by a scanning electron microscope (SEM) in thesame manner as described above in the examples 14 to 18, and accordingto the photograph, the average particle diameter was calculated to findthe average particle diameter was 0.8 μm (reference FIG. 3). Thescanning electron microscope (SEM) photograph is shown in FIG. 14.

[0233] Further, the rod-like zeolite shaped body was subjected to4-point bending strength measurement in the same manner as the examples14 to 18 to find, as shown in Table 4, FIG. 9, and FIG. 10, it was 26MPa.

[0234] Further, as shown in FIG. 11, the disk-like zeolite shaped bodywas subjected to pressure loss measurement in the same manner as theexamples 14 to 18 to find it was 1.8 atmospheric pressure.

[0235] Table 4 collectively shows the results of the measurement for theaverage particle diameter (μm) of the microstructure of the fracturedsurface of each zeolite shaped body obtained in examples 14 to 20 andthe comparative example 16, the four-point bending strength (MPa) andpressure loss (atm) of each zeolite shaped body obtained in examples 14to 20 and the comparative example 16. According to Table 4, the zeoliteshaped bodies obtained in examples 14 to 20 had practically sufficientlylarge average particle diameter and high bending strength as comparedwith those of the zeolite shaped body obtained in the comparativeexample 16 and their pressure loss was found extremely low.Consequently, if a zeolite layered composite comprising a shaped body (asubstrate) with such an extremely low pressure loss just like thezeolite shaped bodies obtained in the examples 14 to 20 and a zeolitemembrane free of defects such as cracks and layered or formed thereon isused as a gas separation membrane of a molecular sieve membrane and apervaporation membrane, the composite can be a highly functional anduseful material with a high flux. TABLE 4 Dried gel production methodZeolite shaped body Mixing ratio to Heating at 4-point total TPA 80° C.,Particle bending Pressure (% by mole) kneading, diameter strength lossΔP TPAOH TPABr drying (μm) (MPa) (atm) Example 14 95.0 5.0 Same above1.5 27 0.9081 Example 15 87.5 12.5 Same above 2.7 22 0.5652 Example 1675.0 25.0 Same above 6.4 13 0.0096 Example 17 62.5 37.5 Same above 8.810 0.0025 Example 18 50.0 50.0 Same above 13.9 8 0.0010 Example 19 — 100Same above 24.0 2 0.0003 Example 20 100 — Spray 7.5 6 0.0006 drying ofsolution Comparative 100 — Heating at 0.8 26 1.8 example 16 80° C.,kneading, drying

EXAMPLE 21 The Second Invention (5)

[0236] A sol for membrane formation of a zeolite membrane was producedby mixing 15.26 g of a 10% tetrapropylammonium hydroxide (TPAOH)solution (produced by Wako Pure Chemical Industries, Ltd.) and 2.00 g oftetrapropylammonium bromide (TPABr) (produced by Wako Pure ChemicalIndustries, Ltd.), further adding 49.85 g of distilled water and 6.00 gof about 30% by weight of silica sol (trade name: Snowtex S, produced byCorporation Nissan Chemical) in such a manner that the mole ratio ofSiO₂/TPAOH/TPABr/water becomes 1/0.25/0.25/125, and stirring theresulting mixture at room temperature for 30 minutes by a magneticstirrer.

[0237] The resulting sol was added to a Teflon inner cylinder-attachedpressure vessel with 100 ml capacity made of a stainless steel and thezeolite shaped body obtained in the example 19 was immersed in the soland reacted for 18 hours in an oven at 180° C. Observation of thefractured surface by a scanning electron microscope (SEM) after thereaction made it clear, as shown in SEM photograph of FIG. 22, that anabout 25 μm thick dense layer was formed on the zeolite shaped body andit was found by x-ray diffraction that the dense membrane was of a MFItype zeolite membrane.

[0238] When the zeolite layered intermediate body obtained as describedabove was heated to 500° C. and kept at the temperature for 4 hours inan electric furnace to remove tetrapropylammonium (TPA), no crack wasobserved by a Rhodamine test and no molecule was found permeating by apervaporation method using triethylbenzene to make it clear that theproduct was a dense zeolite layered composite free of cracks.

EXAMPLE 22 The Second Invention (6)

[0239] A zeolite layered intermediate body was produced on a zeoliteshaped body of the example 20 in the same manner as the example 21.

[0240] When the zeolite layered intermediate body zeolite layeredintermediate body obtained as described above was heated to 500° C. andkept at the temperature for 4 hours in an electric furnace to removetetrapropylammonium (TPA), no crack was observed by a Rhodamine test andno molecule was found permeating by a pervaporation method usingtriethylbenzene to make it clear that the product was a dense zeolitelayered composite free of cracks.

[0241] Incidentally, the cracks caused in the zeolite membrane owing tothermal expansion difference is as small as about 8 to 50 angstrom andcannot be detected even by SEM. Therefore, in the invention, as theabove-mentioned crack measurement method, the following method wasemployed.

[0242] A first method (Rhodamine test) is a method carried out bydropping Rhodamine B on a zeolite membrane and observing the result withan optical microscope.

[0243] A second method (pervaporation method) is a method carried out,as shown in FIG. 15, by sucking triisopropylbenzene (TIPB) molecule 20by a vacuum pump 22 and passing it through a zeolite membrane 21 toobserve the existence of cracks by a vacuum gauge 23 or gaschromatography.

EXAMPLE 23 The Third Invention (1)

[0244] A Teflon beaker of 200 ml capacity was charged with about 30% byweight of silica sol (trade name: Snowtex S, produced by CorporationNissan Chemical) and a 10% tetrapropylammonium hydroxide (TPAOH)solution (produced by Wako Pure Chemical Industries, Ltd.) while themixing ratio (TPA/SiO₂) of TPA (tetrapropylammonium ion) of the TPAOHsolution and SiO₂ being adjusted to be 0.04 by mole and the resultingsolution was stirred at room temperature for 30 minutes by a magneticstirrer and after that, further being heated at 80° C., the resultingsolution was continuously stirred and kneaded manually by a Teflon rodto evaporate water and obtain a colorless dried gel. The obtained driedgel was subjected to x-ray diffraction to investigate the crystalstructure to find it was amorphous.

[0245] The obtained dried gel 100 g was added to a Teflon container of500 ml capacity and mixed with 100 g of distilled water and 1,200 g ofzirconia ball of 5 mm diameter and wet pulverized for 24 hours in a ballmill stand to obtain a slurry.

[0246] As shown in FIG. 23, the particle size of the slurry wasinvestigated by a laser diffraction type particle size distributionmeasurement apparatus (trade name: SALD-2000A manufactured by ShimazuCorporation) to find the particle distribution; 10% volume particlediameter of 0.5 μm, 50% volume particle diameter of 0.9 μm, and 90%volume diameter of 1.8 μm.

[0247] The slurry was passed through meshes of 1,000 μm to separate andrecover zirconia ball mill of 5 mm diameter and stirred by a magneticstirrer.

[0248] The resulting slurry was dried by a spray drier apparatus (tradename: DL-41 model manufactured by Yamato Science Co., Ltd.) inconditions of 1 kgf/cm² spraying air pressure, 0.8 m³/min dried air flowrate, 25 ml/min solution feeding rate, and 180° C. blowing temperatureto obtain a dried gel.

[0249] As shown in FIG. 24, the obtained dried gel granulated powder wasobserved by a scanning electron microscope (SEM) to find the maximumparticle diameter was 40 μm.

[0250] The dried gel granulated powder obtained as described above waspressed by a uniaxial pressing with a die (the entire pressure of 1,000kgf) to obtain a rod-like shaped body of 5×4×40 mm and a disk-likeshaped body of 18 mmφ diameter and 1.8 mm thickness and further shapedby cold isostatic pressing (the entire pressure of 2,500 kgf/cm²) toobtain shaped bodies.

[0251] The obtained each shaped body was set on a Teflon plate so as tokeep each shaped body from water in a Teflon inner cylinder-attachedpressure vessel made of a stainless steel 100 ml and filled withdistilled water in the same weight as that of each shaped body andreaction was caused under spontaneous steam pressure for 10 hours in anoven at 180° C. The shaped body was investigated by x-ray diffractionafter the reaction to be found it was MFI type zeolite. The shaped bodywas sufficiently dried at 80° C. to obtain a zeolite shaped body.

[0252] The microstructure of the zeolite shaped body obtained asdescribed above was observed by scanning electron microscope (SEM) andthe homogeneity was calculated by the photograph to find the area of thesound parts was 100% and as shown in FIG. 25 and FIG. 26, nodegranulation of granules was observed and the microstructure was evenwithout showing non-denseness and denseness in the granule. Further, theaverage particle diameter was found to be 0.8 μm according to the SEMphotograph.

[0253] Further, the rod-like zeolite shaped body was subjected to4-point bending strength measurement according to JIS R 1601 to find itwas 25 MPa. Also, the disk-like zeolite shaped body was subjected topressure loss measurement to find it was 0.18 atmospheric pressure.

EXAMPLE 24 The Third Invention (2)

[0254] A Teflon beaker of 200 ml capacity was charged with about 30% byweight of silica sol (trade name: Snowtex S, produced by CorporationNissan Chemical) and a 10% tetrapropylammonium hydroxide (TPAOH)solution (produced by Wako Pure Chemical Industries, Ltd.) while themixing ratio (TPA/SiO₂) of TPA (tetrapropylammonium ion) of the TPAOHsolution and SiO₂ being adjusted to be 0.04 by mole and the resultingsolution was stirred at room temperature for 30 minutes by a magneticstirrer to obtain a mixed solution of tetrapropylammonium hydroxide(TPAOH) and silica sol for a spray drier. The mixed solution was driedby a spray drier apparatus (trade name: Valvis Mini Spray GA 32 modelmanufactured by Yamato Scientific Co., Ltd.) in conditions of 1 kgf/cm²spraying air pressure, 0.4 m³/min dried air flow rate, 3 ml/min solutionfeeding rate, and 180° C. blowing temperature to obtain a dried gel. Theobtained dried gel was subjected to x-ray diffraction to investigate thecrystal structure to find it was amorphous.

[0255] As shown in FIG. 27, the microstructure of the obtained dried gelwas observed by a scanning electron microscope (SEM) in the same manneras the example 23 to find the maximum particle diameter was 15 μm.

[0256] The dried gel was pressed by a uniaxial pressing with a die (theentire pressure of 1,000 kgf) to obtain a rod-like shaped body of 5×4×40mm and a disk-like shaped body of 18 mmφ diameter and 1.8 mm thicknessand further shaped by cold isostatic pressing (1,000 kgf/cm²) to obtainshaped bodies. The obtained each shaped body was subjected to thereaction in the same manner as the example 23 under spontaneous steampressure for 10 hours in an oven at 180° C.

[0257] The microstructure of the zeolite shaped body was observed byscanning electron microscope (SEM) in the same manner as the example 23to find the area of the sound parts was 100% and as shown in FIG. 28 andFIG. 29, no degranulation of granules was observed and themicrostructure was even without showing non-denseness and denseness inthe granule. Further, according to the SEM photograph, the averageparticle diameter was calculated to find it was 7.5 μm.

[0258] Further, the rod-like zeolite shaped body was subjected to4-point bending strength measurement in the same manner as the example23 to find it was 6 MPa. Also, the disk-like zeolite shaped body wassubjected to pressure loss measurement to find it was 0.6×10⁻³atmospheric pressure.

COMPARATIVE EXAMPLE 17 The Third Invention (3)

[0259] A Teflon beaker of 200 ml capacity was charged with about 30% byweight of silica sol (trade name: Snowtex S, produced by CorporationNissan Chemical) and a 10% tetrapropylammonium hydroxide (TPAOH)solution (produced by Wako Pure Chemical Industries, Ltd.) while themixing ratio (TPA/SiO₂) of TPA (tetrapropylammonium ion) of the TPAOHsolution and SiO₂ being adjusted to be 0.04 by mole and the resultingsolution was stirred at room temperature for 30 minutes by a magneticstirrer and after that, further being heated at 80° C., the solution wascontinuously stirred and kneaded manually by a Teflon rod to evaporatewater and obtain a colorless dried gel. The obtained dried gel wassubjected to x-ray diffraction to investigate the crystal structure tofind it was amorphous.

[0260] The dried gel was pulverized in an agate crucible and passedthrough meshes of 355 μm to obtain an under-mesh powder.

[0261] As shown in FIG. 30, the microstructure of the obtained dried gelwas observed by SEM to find many angular particles of about 50 μm sizeexist.

[0262] The dried gel obtained in such a manner was pressed by a uniaxialpressing with a die (the entire pressure of 1,000 kgf) to obtain arod-like shaped body of 5×4×40 mm and a disk-like shaped body of 18 mmφdiameter and 1.8 mm thickness and further shaped by cold isostaticpressing (1,000 kgf/cm²) to obtain shaped bodies.

[0263] The obtained each shaped body was set on a Teflon plate so as tokeep each shaped body from water in a Teflon inner cylinder-attachedpressure vessel 100 ml made of a stainless steel and filled withdistilled water in the same weight as that of each shaped body andreaction was caused under spontaneous steam pressure for 10 hours in anoven at 180° C. The shaped body was investigated by x-ray diffractionafter the reaction to be found it was MFI type zeolite. The shaped bodywas sufficiently dried at 80° C. to obtain a zeolite shaped body.

[0264] The microstructure of the zeolite shaped body obtained asdescribed above was observed by scanning electron microscope (SEM) andthe homogeneity was calculated according to the photograph to find thearea of the sound parts was 62% and as shown in FIG. 31 and FIG. 32,existence of defects owing to degranulation and partially densifiedportions with granules were observed. Further, the average particlediameter was found to be 0.8 μm according to the SEM photograph.

[0265] Further, the rod-like zeolite shaped body was subjected to4-point bending strength measurement according to JIS R 1601 to find itwas 26 MPa. Also, the disk-like zeolite shaped body was subjected topressure loss measurement to find it was 1.8 atmospheric pressure.

[0266] Table 5 collectively shows the measurement results of thehomogeneity [the area of the sound parts (%)] of the microstructure andthe average particle diameter (μm) of the zeolite shaped bodies obtainedin the examples 23, 24 and the comparative example 17 and the 4-pointbending strength (MPa) and the pressure loss (atm) of the zeolite shapedbodies obtained in the examples 23, 24 and the comparative example 17.

[0267] According to Table 5, as compared with the zeolite shaped bodyobtained in the comparative example 17, the zeolite shaped bodiesobtained in the comparative examples 23, 24 were found to havesignificantly wide area of sound parts (no defect). Further, the averageparticle diameter and the 4-point bending strength were foundpractically sufficiently high and moreover their pressure loss was foundextremely low. Consequently, if a zeolite layered composite comprising ashaped body (a substrate) with such an extremely low pressure loss justlike the zeolite shaped bodies obtained in the examples 23, 24 and azeolite membrane free of defects such as cracks and layered or formedthereon is used as a gas separation membrane of a molecular sieve and apervaporation membrane, the composite can be a highly functional anduseful material with a high flux. TABLE 5 Homogeneity of Average 4-pointmicrostructure [the particle bending Pressure area of the sound diameterstrength loss parts (%)] (μm) (MPa) ΔP (atm) Example 23 100 0.3 25 0.18Example 24 100 7.5 6 0.0006 Comparative 62 0.8 26 1.80 example 17

EXAMPLE 25 The Third Invention (4)

[0268] A sol for membrane formation of a zeolite membrane was producedby mixing 15.26 g of a 10% tetrapropylammonium hydroxide (TPAOH)solution (produced by Wako Pure Chemical Industries, Ltd.) and 2.00 g oftetrapropylammonium bromide (TPABr) (produced by Wako Pure ChemicalIndustries, Ltd.), further adding 49.85 g of distilled water and 6.00 gof about 30% by weight of silica sol (trade name: Snowtex S, produced byCorporation Nissan Chemical) in such a manner that the mole ratio ofSiO₂/TPAOH/TPABr/water becomes 1/0.25/0.25/125, and stirring theresulting mixture at room temperature for 30 minutes by a magneticstirrer.

[0269] The resulting sol was added to a Teflon inner cylinder-attachedpressure vessel with 100 ml capacity made of a stainless steel and thezeolite shaped body obtained in the example 23 was immersed in the soland reacted for 18 hours in an oven at 180° C. Observation of thefractured surface by a scanning electron microscope (SEM) after thereaction made it clear, as shown in SEM photograph of FIG. 35, that anabout 25 μm thick dense layer was formed on the zeolite shaped body andit was found by x-ray diffraction that the dense membrane was of a MFItype zeolite membrane.

[0270] When the zeolite layered intermediate body obtained as describedabove was heated to 500° C. and kept at the temperature for 4 hours inan electric furnace to remove tetrapropylammonium (TPA), no crack wasobserved by a Rhodamine test and no molecule was found permeating by apervaporation method using triethylbenzene to make it clear that theproduct was a dense zeolite layered composite free of cracks.

EXAMPLE 26 The Third Invention (5)

[0271] A zeolite layered intermediate body was obtained in the samemanner as the example 25 on the zeolite shaped body obtained in theexample 24.

[0272] When the zeolite layered intermediate body obtained as describedabove was heated to 500° C. and kept at the temperature for 4 hours inan electric furnace to remove tetrapropylammonium (TPA), no crack wasobserved by a Rhodamine test and no molecule was found permeating by apervaporation method using triethylbenzene to make it clear that theproduct was a dense zeolite layered composite free of cracks.

[0273] Industrial Applicability

[0274] As described above, the invention can provide a zeolite shapedbody on which a zeolite membrane can be formed without causing cracking,and satisfactorily reducing pressure loss and maintaining and improvingmechanical strength when it is used as a gas separation membrane of amolecular sieve membrane and a pervaporation membrane and the like; azeolite layered intermediate body comprising the zeolite shaped body anda zeolite membrane containing a template and layered thereon; a zeolitelayered composite produced by calcining the zeolite layered intermediatebody, and their efficient production methods. Consequently, theinvention can efficiently be applicable especially to the fields whereseparation membranes with high fraction capabilities and high catalystcarrying functions are required and fields (e.g., petrochemical, watertreatment, pharmaceutical, and food industrial fields) where highchemical resistance is required.

1. A porous zeolite shaped body of a zeolite, characterized in that saidporous zeolite shaped body is made of a completely crystallized zeolitecomposed of tetrapropylammonium ion (TPA) and silica sol in a mixingratio (TPA/SiO₂) of 0.015 to 0.08 by mole.
 2. A porous zeolite shapedbody of a zeolite, characterized in that the porous zeolite shaped bodyis made of a zeolite still under crystallization and composed oftetrapropylammonium ion (TPA) and silica sol in a mixing ratio(TPA/SiO₂) of 0.02 to 0.12 by mole.
 3. A zeolite intermediate body,characterized in that the zeolite shaped body as claimed in claim 1 orclaim 2 contains further a template, and a template-containing zeolitemembrane having a composition the same as or similar to that of theshaped body is formed thereon.
 4. A zeolite layered composite comprisingsaid zeolite shaped body and said zeolite membrane layered thereon,characterized in that the composite is produced by removing saidtemplate from said zeolite shaped body and said template-containingzeolite membrane by calcining the zeolite layered intermediate body asclaimed in claim
 3. 5. A method for producing a zeolite layeredcomposite, characterized by layering a template-containing zeolitemembrane having a composition the same as or similar to that of azeolite shaped body of a zeolite still under crystallization andcomposed of tetrapropylammonium ion (TPA) and silica sol in a mixingratio (TPA/SiO₂) of 0.015 to 0.08 by mole and containing a templatetherein on said zeolite shaped body, and simultaneously removing thetemplate from said zeolite membrane and said zeolite shaped body bycalcining the resulting layered product to obtain a zeolite layeredcomposite comprising said zeolite shaped body and said zeolite membranelayered thereon.
 6. A method for producing a zeolite layered composite,characterized by layering a template-containing zeolite membrane havinga composition the same as or similar to that of a zeolite shaped body ofa zeolite still under crystallization and composed oftetrapropylammonium ion (TPA) and silica sol in a mixing ratio(TPA/SiO₂) of 0.02 to 0.12 by mole and containing a template therein onsaid zeolite shaped body, and simultaneously removing a template fromsaid zeolite membrane and said zeolite shaped body by calcining theresulting layered product to obtain a zeolite layered compositecomprising said zeolite shaped body and said zeolite membrane layeredthereon.
 7. A porous zeolite shaped body of a zeolite, characterized inthat the porous zeolite shaped body has an average particle diameter of1.0 μm or larger, a bending strength of 1.5 MPa or higher, and adifference in pressure between a feed side and a permeation side of 1.0atmospheric pressure or lower at 10 ml/cm² min of helium gas permeationflux when a thickness of the porous zeolite shaped body is adjusted tobe 1.8 mm
 8. A zeolite layered intermediate body, characterized in thatthe zeolite shaped body as claimed in claim 7 contains, further atemplate and a template-containing zeolite membrane having a compositionthe same as or similar to that of the shaped body is layered thereon. 9.A zeolite layered composite comprising said zeolite shaped body and saidzeolite membrane layered thereon, characterized in that the zeolitelayered composite is formed by removing said template from said zeoliteshaped body and said template-containing zeolite membrane by calciningthe zeolite layered intermediate body as claimed in claim
 8. 10. Amethod for producing a zeolite shaped body, characterized by adding atetrapropylammonium hydroxide (TPAOH) solution and tetrapropylammoniumbromide (TPABr) to silica sol in such a manner that mixing ratios[TPAOH/(TPAOH+TPABr) and TPABr/(TPAOH+TPABr)] of tetrapropylammoniumhydroxide (TPAOH) and tetrapropylammonium bromide (TPABr) to a totalamount of tetrapropylammonium ion (TPA) become 0 to 99% by mole and 1 to100% by mole, respectively to prepare a solution, drying thus preparedsolution by kneading the solution, shaping thus obtained dried gel, andsubjecting thus shaped body to crystallization treatment.
 11. A methodfor producing a zeolite shaped body, characterized by adding atetrapropylammonium hydroxide (TPAOH) solution to silica sol to preparea solution, spraying thus prepared solution to dry, shaping thusobtained dried gel, and subjecting thus shaped body to crystallizationtreatment.
 12. A method for producing a zeolite layered intermediatebody, characterized by adding a tetrapropylammonium hydroxide (TPAOH)solution and tetrapropylammonium bromide (TPABr) to silica sol in such amanner that mixing ratios [TPAOH/(TPAOH+TPABr) and TPABr/(TPAOH+TPABr)]of tetrapropylammonium hydroxide (TPAOH) and tetrapropylammonium bromide(TPABr) to a total amount of tetrapropylammonium ion (TPA) become 0 to99% by mole and 1 to 100%, respectively to prepare a solution, dryingthus prepared solution by kneading the solution, shaping thus obtaineddried gel, subjecting thus shaped product to crystallization treatmentto obtain a zeolite shaped body, immersing said zeolite shaped body in asolution with the same or similar composition as or to said preparedsolution, and forming a template-containing zeolite membrane on saidzeolite shaped body by hydrothermally synthesizing it thereon to producea layered body comprising said zeolite shaped body and saidtemplate-containing zeolite membrane.
 13. A method for producing azeolite layered intermediate body, characterized by adding atetrapropylammonium hydroxide (TPAOH) solution to silica sol, sprayingthus prepared solution to dry, shaping the obtained dried gel,subjecting the shaped product to crystallization treatment to obtain azeolite shaped body, immersing said zeolite shaped body in a solutionhaving the same or similar composition as or to that of said preparedsolution, and forming a template-containing zeolite membrane on thezeolite shaped body by hydrothermally synthesizing it thereon to producea layered body comprising said zeolite shaped body and saidtemplate-containing zeolite membrane.
 14. A method for producing azeolite layered composite, characterized by adding a tetrapropylammoniumhydroxide (TPAOH) solution and tetrapropylammonium bromide (TPABr) tosilica sol in such a manner that the mole ratio of mixing ratios[TPAOH/(TPAOH+TPABr) and TPABr/(TPAOH+TPABr)] of tetrapropylammoniumhydroxide (TPAOH) and tetrapropylammonium bromide (TPABr) to a totalamount of tetrapropylammonium ion (TPA) become 0 to 99% and 1 to 100%,respectively to prepare a solution, drying thus prepared solution bykneading the solution, shaping thus obtained dried gel, subjecting thusshaped product to crystallization treatment to obtain a zeolite shapedbody, immersing said zeolite shaped body in a solution with the same orsimilar composition as or to that of said prepared solution, forming atemplate-containing zeolite membrane on the zeolite shaped body byhydrothermally synthesizing it thereon to produce a layered bodycomprising said zeolite shaped body and said template-containing zeolitemembrane, and then calcining the layered body to simultaneously removingthe template.
 15. A method for producing a zeolite layered composite,characterized by adding a tetrapropylammonium hydroxide (TPAOH) solutionto silica sol to prepare a solution, spraying thus prepared solution todry, shaping thus obtained dried gel, subjecting thus shaped product tocrystallization treatment to obtain a zeolite shaped body, immersingsaid zeolite shaped body in a solution with the same or similarcomposition as or to that of said prepared solution, forming atemplate-containing zeolite membrane on the zeolite shaped body byhydrothermally synthesizing it thereon to produce a layered bodycomprising said zeolite shaped body and said template-containing zeolitemembrane, and then calcining the layered body to simultaneously removingthe template.
 16. A porous zeolite shaped body of a zeolite,characterized in that area of parts (sound parts) where respectiveparticles are clearly observed by grain boundary fracture amongparticles composing the zeolite shaped body in microstructureobservation of the fractured surface of the shaped body occupies 70% ormore in the entire area of the fractured surface.
 17. A zeolite layeredintermediate body, characterized in that the zeolite shaped body asclaimed in claim 16 further contains a template, and atemplate-containing zeolite membrane having a composition same as orsimilar to that of the shaped body is formed on the shaped body.
 18. Azeolite layered composite comprising a zeolite shaped body and a zeolitemembrane formed thereon, characterized in that the zeolite layeredcomposite is produced by removing said template from said zeolite shapedbody and said template-containing zeolite membrane by calcining thezeolite layered intermediate body as claimed in claim
 17. 19. A methodfor producing a zeolite shaped body, characterized by adding atetrapropylammonium hydroxide (TPAOH) solution to silica sol in such amanner that a mixing ratio (TPA/SiO₂) of tetrapropylammonium ion (TPA)to said silica sol becomes 0.015 to 0.08 to prepare a solution, dryingthus prepared solution by kneading the solution, wet pulverizing thusobtained dried gel, spraying thus obtained slurry to dry, shaping thusobtained dried granular substance, and subjecting thus obtainedsubstance to crystallization treatment to obtain a zeolite shaped body.20. A method for producing a zeolite shaped body, characterized byadding a tetrapropylammonium hydroxide (TPAOH) solution to silica sol insuch a manner that a mixing ratio (TPA/SiO₂) of tetrapropylammonium ion(TPA) to said silica sol becomes 0.015 to 0.08 to prepare a solution,spraying thus prepared solution to dry, shaping thus obtained dried gel,and subjecting thus obtained gel to crystallization treatment to obtaina zeolite shaped body.
 21. A method for producing a zeolite layeredintermediate body, characterized by adding a tetrapropylammoniumhydroxide (TPAOH) solution to silica sol in such a manner that a mixingratio (TPA/SiO₂) of tetrapropylammonium ion (TPA) to said silica solbecomes 0.015 to 0.08 to prepare a solution, drying thus preparedsolution by kneading the solution, wet pulverizing thus obtained driedgel, spraying thus obtained slurry to dry, shaping thus obtained driedgranular substance, subjecting thus shaped product to crystallizationtreatment to obtain a zeolite shaped body, immersing said zeolite shapedbody in a solution having the same or similar composition as or to saidprepared solution, and forming a template-containing zeolite membrane onthe zeolite shaped body by hydrothermally synthesizing it thereon toproduce a layered body comprising the zeolite shaped body and thetemplate-containing zeolite membrane.
 22. A method for producing azeolite layered intermediate body characterized by adding atetrapropylammonium hydroxide (TPAOH) solution to silica sol in such amanner that a mixing ratio (TPA/SiO₂) of tetrapropylammonium ion (TPA)to said silica sol becomes 0.015 to 0.08 by mole to prepare a solution,spraying thus prepared solution to dry, shaping the obtained dried gel,subjecting to thus shaped product to crystallization treatment to obtaina zeolite shaped body, immersing said zeolite shaped body in a solutionwith the same or similar composition as or to that of said preparedsolution, and forming a template-containing zeolite membrane on thezeolite shaped body by hydrothermally synthesizing it thereon to producea layered body comprising a zeolite shaped body and atemplate-containing zeolite membrane.
 23. A method for producing azeolite layered composite, characterized by adding a tetrapropylammoniumhydroxide (TPAOH) solution to silica sol in such a manner that a mixingratio (TPA/SiO₂) of tetrapropylammonium ion (TPA) to said silica solbecomes 0.015 to 0.08 to prepare a solution, drying thus preparedsolution by kneading the solution, wet pulverizing thus obtained driedgel, spraying thus obtained slurry to dry, shaping thus obtained driedgranular substance, subjecting thus shaped product to crystallizationtreatment to obtain a zeolite shaped body, immersing said zeolite shapedbody in a solution with the same or similar composition as or to that ofsaid prepared solution, and forming a template-containing zeolitemembrane on the zeolite shaped body by hydrothermally synthesizing itthereon to produce a layered body comprising a zeolite shaped body and atemplate-containing zeolite membrane, and then simultaneously removing atemplate by calcining the layered body.
 24. A method for producing azeolite layered composite, characterized by adding a tetrapropylammoniumhydroxide (TPAOH) solution to silica sol in such a manner that a mixingratio (TPA/SiO₂) of tetrapropylammonium ion (TPA) to said silica solbecomes 0.015 to 0.08 to prepare a solution, spraying thus preparedsolution to dry, shaping thus obtained dried gel, subjecting thus shapedproduct to crystallization treatment to obtain a zeolite shaped body,immersing said zeolite shaped body in a solution with the same orsimilar composition as or to that of said prepared solution, forming atemplate-containing zeolite membrane on the zeolite shaped body byhydrothermally synthesizing it thereon to produce a layered bodycomprising a zeolite shaped body and a template-containing zeolitemembrane, and then simultaneously removing a template by calcining thelayered body.